Mr and Mrs Smith producer Arnon Milchan claims that Brad Pitt's romance with Angelina Jolie started while he was still married to Jennifer Aniston.

Jolie has always denied that she got involved with the actor while he was still married but according to a new book, Milchan says Pitt was already smitten by Lara Croft star and started romancing her while working on the movie.

He eventually confessed his love for Jolie to wife Aniston, who threw him out of their Beverly Hills home. The couple later got divorce after five-years of marriage.

The 66-year-old Milchan has revealed about the estranged couple in his recently launched book Confidential: The Life of Secret Agent Turned Hollywood Tycoon, Daily Mail reported.

"At first, Jen didn't believe he was involved with Angelina. She started asking around but no one would tell her anything because they were loyal to Brad, so she asked him point blank. He denied it.

"He eventually admitted he was in love with Angelina. Jen was furious and threw him out," authors Meir Doran and Joseph Gelman write quoting Milchan.

The producer originally planned to cast Pitt with Nicole Kidman as the married spy couple for Mr and Mrs Smith but Pitt pulled out of the project, saying they lacked chemistry.

But the actor was already smitten with Jolie and decided to do the project after she was finalised as female lead.

Pitt and Jolie, branded as Brangelina in Hollywood, have three biological and three adopted children.

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