Orochimaru, by far. His theme was better (even if we haven't heard Jubi jin Madara or Kaguya's 'themes' yet; Orochimaru's will still likely be better), his personality was very Joker-like and people IRL legitimately hate him because of how evil he is/was - that's the true sign of a great villain, imo.
The fact that Orochimaru garners so much hate on the Base and in Japan is a testament to how great a villain he is.