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Night March of Kalkamedes
I know others have said it, but it is likely the best PFS scenario I've played. I'm looking forward to GMing it soon. I anticipate liking it just as much from the other side of the screen.
Sniper in the Deep was also a lot of fun, but that one can be quite deadly.
The Disappeared is great for a group focused on stealth and trickery. One is advised to remember where you are going and think about that before entry.
The Confirmation is one that everyone should play. Having now looked at GMing it, the preparation seems a little steep and it uses way too many different resources. I need to go over it more, figure out what I really need in order to be able to run it.

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Night March of Kalkamedes! In my opinion it's pretty much the perfect scenario. It has a lot of amazing shenanigens, a variety of challenges for everyone, an amazing story, an amazing set of BBEGs, an awesome potential love interest/ally for RPs at the end, an EPIC feel, and one of the best Chronicle Sheets rewards I've ever seen. It's also one of the few "babysitting" style scenarios I've seen done really well and that does not begin to irritate the Player, (not character).
The original 4 Blakros Museum Scenarios, Mists of Mwangi, Voice in the Void, The Penumbral Accords, and Echoes of the Overwatched, (especially if the DM doesn't play Nigel as an incompetent ass like some seem to do, and more as a reoccurring NPC friend). Not Matrimony or Silver Mount, though.
God's Market Gamble is also amazing. Like Night Marches, it has a little bit of an RP reward for Good characters, but challenging and fun.
Veteran's Vault is pretty good too, and tends to run a bit short.
Silent Tide and Frozen Fingers of Midnight both have an epic feel and great story, but sadly just don't hold up to the new rules. Both however, if updated, would be contenders for a #2 slot after Night Marches.

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Ye gods, so, so many...
My personal top 5:
#2-16 The Flesh Collector
- Amazing to play, and even more amazing to GM. I had players in tears, and at least two of them made major changes to their characters based solely on events that took place during that scenario. It's also one of the few scenarios where the PCs learn everything that's in the scenario's backstory during the scenario.
(Tie:)
#5-13 Weapon in the Rift
#6-07 Valley of Veiled Flame
- My two favorites (so far) from Seasons 5 and 6 (which I decided on before I knew they were written by the same author!). Great depth-of-story, lots of neat world-story information comes up in both, and the "pace" of both are perfect for what they are. One is an exciting race against time and overwhelming evil, and the other is a fantastic journey through a town shrouded from the rest of the world.
#5-SP Siege of the Diamond City
- Especially at GenCon, but also in the other times I've played/run it since (and used GM star credit on it since I loved it so much) this has such an amazing "feel" to it - run correctly, you can actually feel the tension and chaos in the room, and if you've got the digital map/layers projected on a screen and sound effects for the "house" as well, it can feel pretty epic!
#1-38 No Plunder No Pay
- On this list simply because my first/"main" character in PFS is a pirate, and being able to use his own ship, be piratey in the name of the society, *and* (in my case) shoot his way out from the belly of a sea monster...it was one of the most epic scenarios I've ever played!
#2-13 Murder on the Throaty Mermaid
- Some of the most fun RP I've ever had in my life, and the scenario is *never* the same twice, no matter how many times you might play or GM it!
(Honorable Mention, 1/season:)
#0-13 Prince of Augustana - I highly recommend this one for new players and new GMs. It has fun RP and combat both!
#1-35 Voice in the Void - High creep factor, highly amusing, and lots of variety!
(Tie) #2-25 You Only Die Twice - Unique situations, great RP, and monsters that show up nowhere else that I'm aware of in PFS (including one that looks like it's right out of Dune).
(Tie) #2-02 Before the Dawn pt. 2 Rescue at Azlant Ridge - Once you've played it, you'll know why this one gets mentioned!
#3-02 Sewer Dragons of Absalom - Neat RP, especially if you like subtlety, nicely scaled combats (except for one that can sometimes be a *real* doozy), and lots of chances for a GM to make things really light-hearted and fun even while fighting.
#4-19 Night March of Kalkamedes - A fantastic scenario for newer characters. This scenario almost literally gives the PCs just enough rope to hang themselves with several times, and if the GM is crafty, the roleplay near the end can be really unique.
#5-14 Day of the Demon - Even after it was no longer the Season 4 "Exclusive" scenario, I think I've GM'ed this one almost a dozen times by now. *Very* high on the creep factor, great RP, and combats that are the sort that might be talked about for a long while afterward.
Full Module - The Midnight Mirror - Rather than me ramble even more, the review I wrote for this one is Here.
(Tie) Free RPG Module - We Be Goblins! - Goblins. 'Nuff said!
(Tie) Free RPG Module - We Be Goblins Too! - More Goblins!
I know that's quite a few there...but, what can I say...I really like a lot of the PFS scenarios to-date!

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Rather than stating just a name out of the blue, I'd rather try and set some categories, since someone's favorite scenario may be someone else's bane. Here goes:
Favorite scenarios, by category:
#action: 4-26 The Waking Rune
#epic factor: 2-02 Before the Dawn, part 2: Rescue at Azlant Ridge / 5-13 Weapon in the Rift
#infliltration: 4-11 The Disappeared / 5-11 Library of the Lion
#lore: 5-13 Weapon in the Rift
#mechanics: 5-11 Library of the Lion
#originality: 4-19 The Night March of Kalkamedes
#roleplaying: 4-09 The Blakros Matrimony
#season 0: 0-01 Silent Tide
#season 1: 1-51 City of Strangers, Part 1 - The Shadow Gambit
#season 2: 2-25 You Only Die Twice
#season 3: 3-21 The Temple of Empyreal Enlightenment
#season 4: 4-19 The Night March of Kalkamedes
#season 5: 5-09 The Traitor's Lodge
#season 6 (so far): 6-04 Beacon Below / 6-10 The Wounded Wisp
#special: 6-00 Legacy of the Stonelords
#story: 5-14 Day of the Demon
Best story arc:
Desimire Arc (4-09, 4-11, 4-13, 5-14, 5-25)

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Hmm, lots of options. I enjoyed running the Echoes of the Everwar series although part 4 was a let down. Golemworks was great although I was sad I ran it at low tier as the first time you meet Black its a walk over. I am prepping Below the Silver Tarn at the moment and it looks like a doozy. I want to run Sealed Gate at some point as I enjoyed playing it, I just hope the party is prepared. Blackros Matrimony is excellent with the right group although the last encounter includes some of my least favourite mechanics and when faction missions were a thing there was a very annoying clash with Shadow Lodge.

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From season 0 - Mists of Mwangi
From season 1 - Delirium's Tangle
From season 2 - Murder on the Throaty Mermaid
From season 3 - The Temple of Empyreal Enlightenment
From season 4 - Way of the Kirin
From season 5 - The Paths we Choose
I've hardly played any of season 6 yet, so can't really comment on it. There are lots of other scenarios out there that I really like, but that's one from each season. Temple of Empyreal Enlightenment is probably still my favourite PFS scenario.

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Yet another vote for Night March of Kalkamedes. I thought it was pretty amusing as we stumbled along.
Weapon in the Rift was the one that felt like I was most actively contributing to the war on the World Wound.
I know a lot of people didn't, but I liked both of the Lantern Lodge and Shadow lodge ending scenarios.

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For mine, I'd have to go with Sewer Dragons of Absalom being my absolute favourite, as many have pointed out, it can be light-hearted in the most dire situations, the RP is just funny with the right GM and set of like-minded, or off the wall players...
Another fave of mine was Slave Ships of Absalom...
I also fancy Slave Master's Mirror and Weapon in the Rift because they can be plain good old hack and slash fun with a little bit of preparation and forethought... I know that seems like an oxymoron, but we are murder hobos, no?

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Lesse, there are so many great ones!
Frostfur Captives... So much fun!
The Stranger Within (to me, a perfectly balanced scenario, plus my first GenCon experience when I ran it)
Requiem for the Red Raven -- so good on so many levels, both to play and run!
Murder on the Throaty Mermaid
Gods Market Gamble
I could go on, and I agree with many of the choices above (like Night Marches!)

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I'll go by season since I have to do something to constrain myself.
Season 0: Black Waters
Take the time to really sell the setting to the players, and it will really resonate. The encounters aren't flashy or up-to-date with power creep, but they fit the story completely.
Season 1: Hall of Drunken Heroes
Great story, great setting, and memorable encounters
Season 2: Beneath the Silver Tarn
Perfect balance of role-playing and combat, and everything that happens is connected to the story
Season 3: The Golden Serpent
One of my favorite adventure beginnings, and a great dungeon crawl. Make sure you have tons of time, though.
Season 4: Night March of Kalkamedes
I don't really have anything to add that hasn't already been said.
Season 5: The Traitor's Lodge
Valais is brilliant. The setting is brilliant. The story connections are brilliant.
Season 6: The Slave Master's Mirror
I've only prepped this to run next month so far, but it's already one of my favorites.
As a special shout-out, anything written by Jim Groves (Haunting of Hinojai, The Golden Serpent, The Green Market, The Frostfur Captives...it's all good). I haven't yet played all of Crystal Frasier's scenarios, so I can't yet give her a perfect batting average, but she's up there, too.

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Mists of Mwagi and Voice in the Void - sometimes you just have to go check in on Nigel
Night March of Kalkamedes - extremely memorable, cool chronicle sheet
Valley of the Veiled Flame - has links to another scenario on my list and is a very cool scenario, same author as Weapon in the Rift which is also very good.

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#16: To Scale the Dragon
#40: Hall of Drunken Heroes
#43: The Pallid Plague
#46: Eyes of the Ten, Part 1
#2-05: Eyes of the Ten, Part 3
#2-12: Below the Silver Tarn
#2-13: Murder on the Throaty Mermaid
#3-01: The Frostfur Captives
#3-02: Sewer Dragons of Absalom
#3-05: Tide of Twilight
#3-13: Quest for Perfection, Part 3
#3-15: The Haunting of Hinojai
#3-17: Red Harvest
#3-20: The Rats of Round Mountain, Part 1
#3-22: The Rats of Round Mountain, Part 2
#3-25: Storming the Diamond Gate
#4-03: The Golemworks Incident
#4-07: Severing Ties
#4-09: The Blakros Matrimony
#4-11: The Disappeared
#4-13: Fortress of the Nail
#4-19: The Night March of Kalkamedes
#4-25: Glories of the Past, Part 3
#5-04: The Stolen Heir
#5-09: The Traitor's Lodge
#5-11: Library of the Lion
#5-13: Weapon in the Rift
#5-15: Destiny of the Sands, Part 2
#5-19: The Horn of Aroden
#5-22: Scars of the Third Crusade
#6-01: Trial by Machine
#6-03: The Technic Siege
#6-05: Slave Ships of Absalom
#6-08: The Segang Expedition
Well, that turned into a long list.

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Season 6 is very brilliant so far!
Trial by machine can be hard for some level 1 groups, so can be Silver Mount Collection, but the scenarios are a lot more consistent and NPC´s fleshed out and have really exciting stories!
Segang expedition is the first one where i would say the new season gets a cakewalk on tier 1-2.
Trial by machine is actually one of my favorites so far. It has many funny encounters and shows some challenges in a new and exciting way, but also because of the location and how it is presented.

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Top 3 Favs;
The Crypt of the Everflame series; Good storyline, good options for role-play, and somewhat challenging. Lost my first ever perma-dead character in the first one, and then in the 3rd module the revenge character came THIS CLOSE to also perma-dying...but it was awesome anyway.
Siege of the Diamond City; This is mostly for bragging rights. We did the high-tier with a healer, a fighter, an invulnerable rager, and Tim the Invisible Enchanter (Ezren pre-gen). We all survived, although my fighter now has a deep and personal hatred of being grappled.
We Be Goblins; Because GOBLINS! FIRE! MAYHEM!

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By Season:
0-13: Prince of Augustana
1-39: Citadel of Flame
2-10: Fury of the Fiend
3-01: Frostfur Captives
4-19: Nightmarch of Kalkamedes
5-12/15/16: Destiny of the Sands Series
6-03: The Technic Siege

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Hmm
Season 0, Mists of Mwangi
Season 1, The Devil We Know series.
Season 2 Strangely enough, I've not played many of them. The Bloodcove disguise is one I did play, and enjoyed it.
Season 3 Quest for Perfection*
Season 4 Nightmarch, The Disappeared** Fortress of the Nail***
Season 5 The Stolen Heir (for making Andoran players squirm) The Confirmation (My Janeira has a Kathy Bates/Misery crush on Kreighton Shane), Library of the Lion.
Season 6 So far Valley of the Veiled FLame.
And now the footnotes.
*
**
And end it with, "if discovered, the Ten will disavow all knowledge of your team." Complete with the music playing in the background.
I then cue up the plot when the party tackles the cypher. Just the first 50 or so seconds though.
***

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I really, really like PFS #4-09 The Blakros Matrimony for a whole raft of reasons, ranging from campaign meta-plot to roleplaying opportunities for the players and GM.
I like this one because it encourages the players to all go with their light fluffy roleplaying characters taking them through an engaging completely combat-less scenario until the very end... where it mercilessly slaughters them all with ruthless overamped combats. I can see the author laughing as they wrote this, ha take that for not playing a powergaming murder-hobo.
Some of the scenarios I actually like include the voice in the void, the mists of mwangi, the frozen fingers of midnight, black waters, the devil you know series, murder on a throaty mermaid, the temple of empyreal enlightenment, sniper in the deep, echoes of the overwatched...
Hmm I noticed no season 5 or 6 scenarios came to mind. I've played nearly all of season 5-6, most of it was passably decent, but nothing really super memorable. There's several that I really disliked, let's see. Ah, cairn of shadows was a good one, I also liked the seagang expedition.

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Hmm
Season 0, Mists of Mwangi
Season 1, The Devil We Know series.
Season 2 Strangely enough, I've not played many of them. The Bloodcove disguise is one I did play, and enjoyed it.
Season 3 Quest for Perfection*
Season 4 Nightmarch, The Disappeared** Fortress of the Nail***
Season 5 The Stolen Heir (for making Andoran players squirm) The Confirmation (My Janeira has a Kathy Bates/Misery crush on Kreighton Shane), Library of the Lion.
Season 6 So far Valley of the Veiled FLame.
And now the footnotes.
*** spoiler omitted ****** spoiler omitted **
***** spoiler omitted **
The table I was at when we were playing through Quest for Perfection immediately caught on to the scenario's inspiration without any prompting from the GM. Then again, I had watched the movie this summer on netflix.
While I liked The Disappeared I felt like I had done it far too early for my character. It was something that should have been a capstone, like marking the transition from level 4 to level 5. That's what Quest for Perfection ended up being.

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I really, really like PFS #4-09 The Blakros Matrimony for a whole raft of reasons, ranging from campaign meta-plot to roleplaying opportunities for the players and GM.
Seconded. If you're at all into doing some RP it's way too fun.
-Part 1 and Part 3 of the Quest for Perfection (2 is fun enough but not as good) are really awesome. My favorite one to run and one of my favorite pfs experiences
-The Segang Expedition from the new season was a lot of fun
-You Have What You Hold was also really good

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I just feel the need to throw more kudos and love towards Season 6:
#6-18 From Under Ice just edged out #6-07 for my favorite Season 6 scenario to-date by the barest of margins (thin ice, that :P)
and
#6-19 Test of Tar Kuata was a really fun trip with unique NPCs and enemies that I don't think have ever shown up in PFS before. At least the way the GM handled it, the RP and tasks at the outset were really fun, even (especially?) with half the group flailing their way through some of them!

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Waking rune (hard core mode) was a blast. We had a preset table and went expecting the book to be thrown at us. My bloatmage spent over 6000 gp on consumables and that may have been about par for the course with the other players at the table. I may have broke even on my investment, but it was totally worth it to get to play at that level and not loose a single player.

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For me:
Quest for Perfection (Esp. part 3, but good whole storyline)After running it:
** spoiler omitted **
You my friend need to read the Succubus in a Grapple Thread.
Waking rune (hard core mode) was a blast. We had a preset table and went expecting the book to be thrown at us. My bloatmage spent over 6000 gp on consumables and that may have been about par for the course with the other players at the table. I may have broke even on my investment, but it was totally worth it to get to play at that level and not loose a single player.
I am burning a GM star to replay Hard Mode with another character. I think I've a fair chance of kicking his ass royally the second time.

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In order from most Recently released to Oldest, Bolding the very favorites:
6-15 The Overflow Archives
6-13 Of Kirin and Kraken
Season 5 Special: Siege of the Diamond City
5-15 Destiny of the Sands Part 2: Race to Seeker’s Folly
5-14 Day of the Demon
5-11 Library of the Lion
4-26 The Waking Rune
4-19 Night March of Kalkamedes
4-11 The Disappeared
4-09 The Blakros Matrimony
4-03 The Golemworks Incident
3-26 The Portal of the Sacred Rune
3-10 The Immortal Conundrum
3-02 Sewer Dragons of Absalom
3-01 The Frostfur Captives
2-25 You Only Die Twice
2-22 Eyes of the Ten Part 4: Nothing Ventured Nothing Gained
2-16 The Flesh Collector
2-02 Before the Dawn Part 2: Rescue at Azlant Ridge
46 Eyes of the Ten Part 1: Requiem for the Red Raven
40 Hall of Drunken Heroes
6 Black Waters
5 Mists of Mwangi