The Hustle star, 45, is set to portray Kalinda's (Archie Panjabi) estranged husband, reports TV Line.
Warren's character is described as dangerous and manipulative, who Kalinda ran away from but will be reconnected at the start of The Good Wife's upcoming fourth season.
On The Good Wife, Kalinda is a private investigator who had an affair with Alicia's (Julianna Margulies) husband (Chris Noth), which eventually ended her friendship with Alicia.
ER alum Maura Tierney was recently cast as a self-made billionaire, who is being sought by Eli (Alan Cumming) to fund and endorse Peter's campaign.
The Good Wife will return to CBS on Sundays at 9/8c in the fall. The series airs on More4 in the UK.
Watch a clip of The Good Wife below: