Strictly speaking, the first super villain was Fantomas (created 由 the French 作者 Paul Féval in 1862). However, the first super villain in a comic book is considered as being the Ultra-Humanite (Action Comics #13, June 1939)
If 你 look at it technically, and 你 surmise that 超人 is the first "Superhero" then 你 must not know that 超人 was actually originally the very first "Super Villain". In 1933 Siegel actually wrote 超人 as a super human version of Lex Luthor. Hope that helps :)
