Well I have two. My first was a lvl 18 Cleric of Sune. I started as an ethos cleric with the Death and Destruction domains... but our group go sucked into Ravenloft. After being in that place my character actually went from CN to CG and had the oportunity to become the chosen of one of 3 gods. You see we had torn a rift into FR letting Ravenloft seep into FR. Sune, a dwarven god, and an elven god decided to come down and offer thier blessing to me and the dwarven cleric. He of course chose the dwarf god. I had some nature god or Sune. I chose Sune. Now after her blessing I had a CHarisma somewhere in the 50's. I played him bullheaded and stuburn. Over the course of the game I started a warlike sect of Sune, caused a rivalry with the church of Kord, and somehow caused Sune to gain the war domain lol. Arguing directly with my God was a daily event. I even won a few lol.
My second was a Planar Shepard that reached the high teens. We where playing a 3.5 game based in the WOW RPG. My character and My brother where the last remaining nobility that survived from Stramguard. We ended up returning to rebuild the kindom. I chose the plane that Demons and Angles fight each other every day. So I could shift into Angles. Favorite moment. We where meeting with the last of the Stramguard Knights to convince them to join us. During the meeting an Assassin killed thier leader and runs out into the crowd waiting outside. I run outside, shift into a Archon and Holy Worded the croud. Now unkown to me a dozen or so assassins and spies had entered thier order... so a dozen people in the croud just dropped dead on the spot... 3 or four stunned and blinded lol. All turned out to be evil... well exept for the Knights um... Interrogator... he was a good guy... just not the best of alignments lol.
The assassin ended up killing my brother but we got him. That left my character the last remaining heir to the thrown. We ended up establishing a new kindom seperate from the alliance or horde. Was a fun game.
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In 3.5 I had a cohort who was an 18th level Bard/Sublime Chord/Archmage. Interesting because my GM chose my cohort. I wanted anything but a gnome bard and he game me a human bard who was promtly killed and reincarnated as a gnome. I was pulling for Bugbear. In any case sublime chord redeemed his usefullness and he eventually made it all of the way to archmage and turned himself back into a human. He liked to use shaped prismatic sprays as his favored attack form and took out quite a few powerfull enemies that way in our Age of Worms Campaign.
My favorite high-level caster is the namesake of my user name here on the Paizo boards, an elf enchantress (controller subspec) who was probably the most infamous person on the homebrew world she originated in. Vain, proud to the point that she believed she was better and more deserving of having "her way" than any deity, and drop-dead gorgeous, she was extremely persuasive and divisive in a "love her or hate her" sort of way.
The most amusing incident with it was just after she hit 20th level and got her capstone Force of Will power. Ansha had gotten it in her head that she wanted silver dragons to guard over the hidden mountain kingdom she had created, so she convinced the party to go to another continent to find several silver dragon eggs. Now, the dragons on this continent weren't necessarily evil, but they had serious superiority issues (all humanoids were cattle, essentially), and so when the clans of Gold Dragons became a nuisance, she led the party in an attack on their leader. After killing the leader, they went outside the leader's lair and confronted a good half-dozen Huge or larger gold dragons intent on avenging him.
So she cast Overwhelming Presence. Every one of the dragons bowed to her as if she were a deity and were promptly finished off by the melee types. The funny thing is that several of the dragons had made their save, but Force of Will's capstone makes Overwhelming Presence a guaranteed one round of helplessness.
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RPG Superstar 2013 Top 32
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My most interesting high-level caster character was probably Esper, an air genasi Abjurer/Incantatrix who specialized in dealing with outsiders. He ended up joining the Harper's Guild (Forgotten Realms) and was pretty instrumental in completely preventing a demonic invasion of epic proportions. I believe at endgame he was something like Abjurer 5/Incantatrix 10/Archmage 2. This was in 3.5 of course, using the original Incantatrix PrC from Magic of Faerun before they revised it in the Player's Guide.