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The first supervillain to regularly battle a superhero was the Ultra-Humanite, who first appeared in Action Comics # 13 ( 1939 ).

In contrast to the super-strong Superman, he was a crippled and bald genius, and could be seen as one of the first examples of the evil genius archetype, due to his deformed body and baldness.

However another potential is the Batman foe Doctor Death, an evil Scientist who used poisons.

He appeared in Detective Comics # 29 ( July 1939 ) and # 30 ( August 1939 ), however these were his only Golden Age appearances.