Entertainment Weekly reports that Lundgren - most famous for his role as Ivan Drago in Rocky IV - will likely play a villain in the episode.
Chuck creator Josh Schwartz teased the actor's appearance on his Twitter account, writing: “It’s true. Dolph [will] try and ‘break’ Chuck in Season 4 premiere.”
The action star will return to the big screen for the first time in 15 years in Sylvester Stallone's upcoming blockbuster The Expendables.
Alien actor Harry Dean Stanton will also appear in the Chuck instalment, titled 'Chuck vs. the Anniversary'.
Stanton recently appeared in a recurring role on HBO drama Big Love.
Chuck will return to NBC for a new season in September.