The Amazing Spider-Man #013 (1964)
“The Menace of Mysterio!”
Writer: Stan Lee
Artist: Steve Ditko
The 1st appearance of Mysterio. Mysterio impersonates Spider-Man and commits a crime. Spider-Man finds him and they fight. Mysterio gets the better of him. Spider-Man finds him at a movie studio and finds out he used to be a stunt man and defeats him.