The Amazing Spider-Man Annual #01 (1964)
“The Sinister Six!”
Writer: Stan Lee
Artist: Steve Ditko
Dr. Octopus gets out of jail and forms the Sinister Six. The team of villains includes Mysterio, Electro, Kraven, Sandman, The Vulture, and (obviously) Dr. Octopus. They make a plan to take down Spider-Man, but it doesn’t work and Spider-Man beats them all.