The network confirmed in July that it had ordered 13 episodes of the show.
Smith will take on the role of Director Higgins, played in the original pilot by Stephen Rea. The recasting was apparently a joint decision between CBS and 20th Century Fox TV.
The character is described as the "manipulative but calm" director of the Clandestine Administration and Oversight Services who recruits rookie CIA agent Rick Martinez (Freddy Rodriguez).
Smith is known for his role as Red Forman on Fox sitcom That '70s Show and has also featured in recurring roles on 24 and Medium.
Chaos is expected to debut on CBS as a midseason replacement.