Stacy Keach will also join him in the director's follow-up to The Descendants, reports Go.
The pair will join Bruce Dern and Will Forte, who will star in the black-and-white road trip movie.
Dern will play an ornery, alcoholic father who convinces his son (Forte) to journey across the country with him to claim a sweepstakes prize.
Odenkirk will play Forte's older brother, with Keach appearing as a long-time colleague of Dern's cantankerous character.
On top of a recurring role in Breaking Bad, Odenkirk will feature in forthcoming movie The Spectacular Now.
Keach most recently appeared in The Bourne Legacy and will next be seen in The Architect.