Iron Man.  Best anime:  Justice League:  Doom.  Or the first Burton Batman for the great Batman vs Joker chemistry, if you like villain drama.  Though the Gene Hackman Lex Luthor was unforgettable and Heath Ledger joker will probably change all the future Jokers.

Runners up:  Elektra, or, the 2009 Wonder Woman anime.  Both sadly overlooked.  Or Batman Returns for the two great villains.  Spider-Man 2 and Captain America:  First Avenger also not bad.  And Tom Huddlesworth Loki probably also redefines that villain.