As a subject matter expert in comic book history, I can tell you that the first villain Spider-Man ever faced was the Chameleon. The Chameleon, whose real name is Dmitri Smerdyakov, made his first appearance in "The Amazing Spider-Man" #1 in 1963. He is known for his ability to disguise himself by using a suit that can change its appearance to mimic anyone he chooses.

However, it's important to note that the Chameleon is not typically considered Spider-Man's arch-nemesis. That title is often given to Doctor Octopus, also known as Dr. Otto Octavius. Doctor Octopus first appeared in "The Amazing Spider-Man" #3 in 1963, just a couple of issues after Spider-Man's debut. With his four mechanical tentacles and his role as a brilliant scientist turned villain, Doctor Octopus has been a constant and formidable foe for Spider-Man throughout the character's history.

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The Amazing Spider-Man debutsSupervillain nameNotable alter egoFirst appearance issue #VultureAdrian Toomes Blackie Drago#2 (May 1963)TinkererPhineas Mason#2 (May 1963)Doctor OctopusDoctor Otto Gunther Octavius#3 (July 1963)SandmanWilliam Baker / Flint Marko#4 (September 1963)52 more rowsread more >>