The Good Will Hunting star will go bald to play the 34th leader of the United States, while Melissa Leo is slated to portray his wife Mamie, according to The Hollywood Reporter.
The film is based on the true story of White House domestic worker Eugene Allen, who served under eight First Families.
Williams joins an all-star cast, which features Forest Whitaker in the lead role, Minka Kelly as Jackie Kennedy Onassis, and Alan Rickman and Jane Fonda portraying Ronald and Nancy Reagan.
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The project is set for a 2013 release.
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