Williams, 29, will play the wannabe star-turned-murderess for a limited run in the hit musical from Feb. 8 to March 28.
Williams will be taking over from Ashlee Simpson-Wentz, who debuted in the revival on Dec. 1. (A winner of six Tonys, this production of Chicago has been running on Broadway for 13 years.)
Williams first played Roxie last year in London's West End production.
Williams, who won three Grammy Awards while she was with Destiny’s Child, has since released three solo albums and in 2003 made her Broadway debut in Aida, replacing fellow singer Toni Braxton. She also performed in the national tour of The Color Purple.