Entertainment Weekly says that the actor will appear in the sixth episode of the upcoming third season.
The show's executive producer Jeff Eastin explained that Silverman will play "a bad guy who is working with a black widow".
He added: "They're working together to kill rich guys and steal their fortunes."
Silverman appeared in the movie Weekend at Bernie's and has previously guest starred in shows including Friends, Psych, Medium and Greek.
Other actors who have already signed up to appear in the third season of White Collar include Moran Atias, Jayne Atkinson, William Sadler, Anna Chlumsky and Neil Jackson.