The two are set to play husband and wife in the Ryan Murphy film.
Pitt's partner actress Angelina Jolie is however ‘quite concerned’ over the onscreen reunion.
The film is about the wife of Richard Nixon's attorney general defending her husband after the Watergate scandal.
The film also stars Meryl Streep and Sharon Stone and is written by John Jeter.
Gwyneth and Pitt got engaged in 1997 and their relationship was much publicized, just like their break-up two years later after he left her for his ex-wife Jennifer Aniston.
Gwyneth is currently married to Coldplay frontman Chris Martin, with whom she has two kids.
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