1) Luke in RotJ (for all of 5 minutes) as he destroys Vader with the Dark Side
2) Lex Luthor in Smallville. Others may not agree, but he's been our favourite character on the show (early seasons, at least) and we really enjoyed seeing the seeds of his future dark side being sown. At some point it seems that he became the typical villain, but up until then he was really interesting.
Who/What else?
xhonzi