The rivalry between Spider-Man and Doctor Octopus is long and well-documented, spanning six decades. The two characters have been locked in a heated battle of wills ever since their first meeting in 1963, with each emerging victorious over the other on various occasions over the decades. As the hero of the story, Spider-Man usually manages to defeat Doctor Octopus in their frequent skirmishes, but that hasn't kept the villainous octopod from proving his superiority every now and then.
Source：https://www.cbr.com/spider-man-doctor-octopus-fight-lost-marvel/
