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This one is one I hope to throw at them soon, though they won't know her as anything but the Scarlet Lady for a while.
Her real name is Eleanor Mossbridge. She was an ordinary apprentice mage to a very well known archmage, but she left his tutelage when a group of people asked her to come along with them on an adventure to travel the world. After many dangerous adventures, she gets to trust them like family, and they begin to form a true bond. And shortly after that point...they experience a TPK. Eleanor survives, enslaved by the vampiric lord of their final dungeon crawl, but the rest of her party are slain by daemons, their souls condemned to Abbaddon for all eternity.
Eleanor is inadvertently given her free will again when another band of heroes slays the vampire lord. She flees, and begins to hunt down anything that can get her friends back. She finds one such method: a ritual which creates a temporary planar convergence, bringing the planes of existence within touching distance of one another for the briefest moment. During that moment, she'll snatch their souls back to the Prime Material, restoring them to life and raising them up from perdition. She's desperate, as no attempt at planar travel or resurrection has thus far succeeded, and she is well aware of the potentially horrible consequences, but her love is so strong that she's willing to do anything to bring them back. Of course, they won't know most of this until much, much later. For now, she'll merely be a mysterious and shadowy figure moving horrible people across the world to do her bidding, finding the aspects of the ritual and causing chaos in the process, tearing up cities and entire cultures in their desperate search for the pieces of the ritual.

The Elusive Trout |

This one is one I hope to throw at them soon, though they won't know her as anything but the Scarlet Lady for a while.
Her real name is Eleanor Mossbridge. She was an ordinary apprentice mage to a very well known archmage, but she left his tutelage when a group of people asked her to come along with them on an adventure to travel the world. After many dangerous adventures, she gets to trust them like family, and they begin to form a true bond. And shortly after that point...they experience a TPK. Eleanor survives, enslaved by the vampiric lord of their final dungeon crawl, but the rest of her party are slain by daemons, their souls condemned to Abbaddon for all eternity.
Eleanor is inadvertently given her free will again when another band of heroes slays the vampire lord. She flees, and begins to hunt down anything that can get her friends back. She finds one such method: a ritual which creates a temporary planar convergence, bringing the planes of existence within touching distance of one another for the briefest moment. During that moment, she'll snatch their souls back to the Prime Material, restoring them to life and raising them up from perdition. She's desperate, as no attempt at planar travel or resurrection has thus far succeeded, and she is well aware of the potentially horrible consequences, but her love is so strong that she's willing to do anything to bring them back. Of course, they won't know most of this until much, much later. For now, she'll merely be a mysterious and shadowy figure moving horrible people across the world to do her bidding, finding the aspects of the ritual and causing chaos in the process, tearing up cities and entire cultures in their desperate search for the pieces of the ritual.
Aw... I love villains like this. Redeemable if helped.

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My favorite that I've cooked up (and am planning to unleash) is Kataar.
Backstory: While originally human, Kataar (Then Thomas Gadderly)'s parents were killed while he was an infant. He was saved by the mercy of the chieftain, who caught a glimpse of intelligence in the child. The wisdom of this choice quickly became apparent as he shot through the ranks of the tribe, until at age 13, a paladin army attacked the main city (orcs do have SOME cities in my world), killed everyone he cared about, and left him for dead.
At this point, he heard whispers in the dark. Telling him he could get revenge for the death of his family (at this point, he considers himself an Orc.) and justice for his scattered people. He accepted the deal. His wounds healed. He gained the courage and skill necessary to forge the Orcs into an organized fighting force. It was realized he had the birthmark spoken of in prophecy, and eh took on the mantle of Kataar (Savior in Orc).
Can't decide if he's an antipaladin or Cavalier.

Gluttony |

Had to dig this one up from a really old Facebook post:
One of my favourites was a fellow called 'Mother' Manning (real name Mariano Manning). He started out as a slightly-reclusive sterile druid down on his luck, unloved by all the women of his local area, and desperate for a family of his own. He reached out to the gods, and Lamashtu answered.
The Mother of Monsters filled him with fiendish Thriae larvae, turning his body into a living incubator of sorts and making him essentially the queen of a hive of fiendish thriae devoted to Lamashtu (because Thriae CRs are ridiculously widespread, and the PCs couldn't deal with a true queen). When the PCs first faced him he was a rather creepy NE human druid with waxy holes in his chest, some filled and nurturing growing larvae, some of which would occasionally burst as a larva wriggled out of his body, and some of which gaped open from where larvae had already left. When he was killed, the fiendish larvae still remaining in his body amassed in desperation, causing his head to burst open in a mass of flailing fiendish tentacles, effectively turning him into a Spawning Canker (Adventure Path #46) associated with Lamashtu rather than Shub-Niggurath.
Managed to give 3 out of 4 players nightmares with that one.

Sean O'Brien 794 |
Best I've got so far is one I'm about to run, and it just sort of sprang to me right before I was about to run a homebrew (delaying us slightly while I developed him).
Basically there's a trading center in the PCs' home town run by two criminal merchants. One's your typical sly mob-boss/merchant prince, while the primary competitor is a psychopathic gnome master chymist named Shit Kenter (he coined that first name himself). He's also an amateur gunslinger who practices on a flock of birds he keeps in his house at all times. Unlike most gnomes he was born with literally no talent for magic, which is why he started dabbling in alchemy and gun smithing.
The thing is that even the most modest of local knowledge checks reveals that despite the fact that he's a murderous lunatic, his presence in the trading enclave is the only reason that the main mob-boss offers reasonable prices on any of his goods, meaning that removing him, no matter what he does to the PCs, is a bad call for them. I'm curious to see how they handle it.

ID-TheDemonOfElru |

In one of my campaigns one of the most talked bout villains I ever threw at my party was Pondmuk the Goblin.
My players loved to talk a lot about this campaign and thankfully their preconceptions of "dumb goblins" meant they failed to realise the threat of a smart, evil goblin till it was too late.
Anyway - in a classic adventure scenario the party was trying to help a town out against a tribe of goblins who were on the rampage, they discovered their lair easy enough but on route to the lair they discovered a lone goblin wandering, muttering to himself on the beach. Needless to say they interrogated him, and he fed them a story of how he got kicked out his tribe for "burning down the shamans hut" (no one bothered to use Sense Motive against his story), and that he would gladly help lead them to the lair and tell them what he knows of their defenses, etc. The group was a little wary of him and decided to drag him along to make sure his information is accurate and also so that he wouldn't betray them to his tribe.
So in they went, fighting off the goblins and defeating traps as they went, with almost everything following the information Pondmuk gave them. So they let him go when they went in far enough - Pondmuk left the dungeon promising to lead his own life his way (the players thought he was "cool" and hopes to make him a cohort or companion).
Truth is Pondmuk WAS the Tribe Shaman and got kicked out for burning down his tent as well as several others when he summoned a uncontrolled fire elemental. They kicked him out and he swore revenge on his brethren - but he was also very ambitious.
The group fought tooth and nail through the dungeon, exhausting all of their resources and forcing them to camp Halfway through. On their second push to clear out the reorganized defenders they nearly exhausted their resources again, after felling the Goblin Chieftain. Just as the group was rejoicing in their victory a mob of Kobolds burst into the dungeon (another local tribe that warred with the Goblins, Pondmuk went to them in disguise and told them about the attack and the Kobolds seized on their chance to wipe out their enemies). As the party desperately fought off the first wave they saw an even larger force of Kobolds arrive - led by Pondmuk himself. The party was exhausted, their spells and potions almost all gone and now they face a threat worse than the Goblins they just fought.
The party had no idea what to think until Pondmuk spoke quite clearly and intelligently (showing he was only acting dumb) thanking them for getting revenge for him - and demanding their surrender before he changes his mind. The group was furious at the little double crosser but had little choice but to surrender or be killed. So prisoners they became, and after a time they escaped their Kobold captors and plotted revenge on the little menace who by now had laid waste to the human settlement they were trying to protect in the first place. They discovered he had been appointed "Mayor" of the ruined town with his slew of Kobold guards.
The party still remembers this little guy sooooo long after the adventure, and look back on how they let their preconceived stereotypes get in the way of their characters, now they have learned to never judge a book by its cover but always they remember their favourite villain Pondmuk and how he outsmarted them....