The 36-year-old star will play the part of Avery LeClaire, the stunning cosmetics company boss to Amy Schumer's Renee Bennett, reported Deadline.
The film is written by Kohn and Silverstein, who are also making their directing debut with "I Feel Pretty".
Production on the film will begin in July on the East Coast.
Williams is currently shooting Ridley Scott's "All the Money in the World".
Schumer, who is also a producer on the movie, was last seen in "Snatched".
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