After Spider-Man chases Electro from quarantine to quarantine, eventually cornering him at a local power relay, Black Widow shoots the villain to neutralize him. When Electro's sister, carrying a Symbiote, runs to him, he is overtaken, becoming a monster. After exploding and scattering the quarantine site, Peter awakes to find Widow hovering over him saying he is under arrest.
She later arrives on Ryker's Island in order to apprehend Spider-Man, taking him and Tinkerer into custody. Recruiting the pair, she leaves Spider-Man to defend the safe zone around Stark Tower whilst Tinkerer works on a weapon to defeat the Symbiotes.