anyway, my answer is hands down elfen lied not only are the main "villains" the coolest villains out there, they're very likable at times (except for one) and the alleged heroes are generally the worst of all, which makes for an even better villain still
Get Smart had some humorous ones with its evildoers from Kaos. Mr. Big was one of them (the midget). Then there was Melnick, the smiling killer. The Chief: You'll be looking for Melnick, the smiling killer. Max: You have to give credit to a man who enjoys his work. The Chief: Melnick has been on a hundred straight killing assignments and hasn't failed yet. Max: That's some record. His parents must be proud of him. The Chief: He doesn't have any parents, Max. They were his first assignment. .
Julie Newmar... or Eartha Kitt? or Lee Merriwether? Hehehe uh, realizing that I'm asking who gave you a boner... no homo...