9. Daniel Shaw - Chuck
I thought it was interesting that the first person on this list was Lex Luthor and now Brandon Routh is the second, another villain to the Superman franchise. He wasn't technically a villain but the way he took the part of ruining Superman Returns, I definitely see him as a villain. Chuck was a great show with a lot of villains and Daniel Shaw was the best one. You watch the show, being led to believe that he is on the hero's side and then he reveals himself as the most devious, mastermind villain in the show's history.