Tom Holland stars in the film, which Sony has dated for Dec. 17, 2021, which has Spider-Man: Homecoming and Spider-Man: Far From Home director Jon Watts back at the helm.
Benedict Cumberbatch will appear in the film as Doctor Strange, while Spider-Man mainstays expected to return include Zendaya, Marisa Tomei, Jacob Batalon and Tony Revolori.
Molina's involvement ties together three generations of Spider-Man movies.
Jamie Foxx is returning as Electro after playing the role in 2014's The Amazing Spider-Man 2, which starred Andrew Garfield as the wall crawler, while Molina's Doc Oc terrorized Maguire's version of Spidey.
In October, Foxx suggested in a since-deleted Instagram post that three different Spider-Men could appear in the film.
Marvel and Sony had no comment.
Molina, who earned Emmy and Golden Globe nominations for 2017's Feud: Bette and Joan, starred in Frozen II last year and has Netflix and DreamWorks' Trollhunters: Rise of the Titans due out next year. »