Aldamisa International introduced Sin City: A Dame To Kill For to buyers in Cannes last summer.
Production is underway and Dimension Films will distribute in North America on Oct 4.
The Brolin deal follows Monday’s announcement that Joseph Gordon-Levitt had joined the cast.
Brolin, who stars in Warner Bros’ Firday release Gangster Squad, will play the role of Dwight. A press release described his fate in the film thus: “Dwight is hunted down by the only woman he ever loved, Ava Lord, and then watches his life go straight to hell.”