Soon I Will Be Invincible by Austin Grossman, 287 pages.
Doctor Impossible is a super-genius, a super-villain extraordinaire. He knows many things, among them he knows, in his scared schoolboy heart of hearts is that he will never really take over the world, that he will never really be invincible. He just can't stop trying though. Half of the book is told from his point of view. He is a sweet,sad, angry man, wistful and aware of (and ashamed of) his own flaws and failings, but he has chosen to be a villain, and he is going to see it through.
The other half of the book is told from the point of view of Fatale, newest member of the new Champions. She's a cyborg agent who doesn't remember the details of her life before the accident that led to her transformation. She also has some anger issues. The NSA let her go, and after freelancing for a while, she happy to have joined the newly reformed Champions.
Corefire, leader of the original Champions, may have been a victim of foul play, leading to a showdown between the forces of good and evil.
Smart, self-aware, and always funny. Great on audio, too.