The Breaking Bad star will play a business associate of Cornelius Hawthorne, father of Pierce (Chevy Chase), according to New York Magazine.
Esposito played Gustavo 'Gus' Fring on AMC's Breaking Bad and currently appears on ABC fantasy drama Once Upon a Time.
His film credits include 1992's Malcolm X, 1994's The Usual Suspects and the forthcoming Alex Cross.
Community is currently on hiatus, after NBC dropped the show from its midseason schedule.
However, the network's entertainment chairman Robert Greenblatt has reassured fans that the comedy will return later this year.
A forthcoming episode will spoof NBC's axed crime drama Law & Order.
> Community: Why NBC should save it
Watch the cast of Community in CollegeHumor's 'Save Greendale' video below: