The former Lie to Me star will play a prosecutor and potential love interest for Cary (Matt Czuchry), according to TV Guide.
"We know she'll be amazing across from Matt Czuchry, since they get to work together both professionally, and perhaps more than professionally," said executive producer Michelle King.
Raymund played Ria Torres on Fox's Lie to Me until the show's cancellation, and will appear in the new season of CBS cop drama Blue Bloods.
She has also featured in an episode of Law & Order: Special Victims Unit and will reunite with her Lie to Me co-star Tim Roth in 2012 film Arbitrage.
The Good Wife co-creator Robert King previously hinted that Kalinda (Archie Panjabi) could become attracted to Cary in future episodes of The Good Wife.
"There's something about Cary that is always very important to her, but it's unclear as to whether that's as a brother or a lover," he teased.
The Good Wife returns to CBS on Sunday, September 25 at 9/8c.
> Good Wife exec: 'Kalinda will be more human'
Watch a promo for the new season of The Good Wife below: