Chameleon (comics)
Created by writer Stan Lee and artist Steve Ditko, the character first appeared in "The Amazing Spider-Man" #1 (March 1963), making him the first member of Spider-Man's rogues' gallery, based on issue publication date, excluding the burglar who murdered Ben Parker (Supercharger was the first Spider-Man supervillain chronologically). He is also well known to be related to Kraven the Hunter. That revealed relationship helped evolve him as a major villain compared to his original depiction of being just a solo villain in the original issue of "The Amazing Spider-Man".
Brothers Grimm (comics)
During the "Acts of Vengeance" storyline, the Brothers Grimm are freed from prison by the Wizard. They battle a cosmic-powered Spider-Man and are defeated. Alongside Graviton, Titania, Trapster, and Goliath IV, the Brothers are hired by the Chameleon to kill Spider-Man. They are then tricked into attacking the Kingpin and defeated by Spider-Man. Alongside Mockingbird and the Werewolf, they help the Shroud defeat a street gang.