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85. Mysterio
In 2009, Mysterio was ranked as IGN's 85th Greatest Comic Book Villain of All Time.
Debuting in The Amazing Spider-Man #13, Mysterio is Quentin Beck, a special effects wizard and stunt man working for a major Hollywood studio with dreams of making a name for himself in the film industry. However, he came to see his career in special effects as a dead-end job. His attempts to become an actor were poorly received, but he realized that his expertise in illusions could make him an effective supervillain.
In his first battle with Spider-Man, after he frames him for robbing the Midtown Museum, Mysterio obstructs the hero's spider-sense with gas and dissolves his webbing with a chemical abrasive. However Spider-Man tricked him into revealing he robbed the museum, then revealed he had captured it on tape. Mysterio was then jailed, blaming Spider-Man for his ruined career. He later joins the Sinister Six in an attempt at revenge on Spider-Man, and battles him using robots of the X-Men. After this Spider-Man gets a card that enables him to go on to battle Sandman.

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“Mysterio, who first came on the scene in Amazing Spider-Man #13, has made it his life goal to piss off Spider-Man, and he's done a good job of it. Also known as Quentin Beck-he faked Aunt May's death, scared her into thinking she was being attacked by aliens, convinced Spider-Man he was 6 inches tall using hypnosis and tricked Spidey into believing he killed a guy.After believing Spider-Man was a clone, he turned his interests over to Daredevil. Like Spider-Man, Mysterio's goal was to turn him insane. He almost got him to kill a baby he falsely believed was the Antichrist, convinced Matt Murdock's secretary/love interest Karen Page that she had contracted HIV from her time as a porn star and manipulated Murdoch's law partner Foggy Nelson into having an affair, and then frames him for killi” read more