Brad Pitt

In early 2005, Jolie was involved in a well-publicized Hollywood scandal when she was accused of being the reason for the divorce of actors Brad Pitt and Jennifer Aniston. She and Pitt were alleged to have started an affair in 2004 while filming Mr. & Mrs. Smith (2005). She denied this on several occasions, but admitted that they "fell in love" on the set. In an interview in 2005, she explained, "To be intimate with a married man, when my own father cheated on my mother, is not something I could forgive. I could not look at myself in the morning if I did that. I wouldn't be attracted to a man who would cheat on his wife."

While Jolie and Pitt never publicly commented on the nature of their relationship, speculations continued throughout 2005. The first intimate paparazzi photos emerged in April, one month after Aniston had filed for divorce; they showed Pitt, Jolie and her son Maddox at a beach in Kenya. During the summer Jolie and Pitt were seen together with increasing frequency and most of the entertainment media considered them a couple, dubbing them "Brangelina". On January 11, 2006, Jolie confirmed to People that she was pregnant with Pitt's child and thereby acknowledged their relationship for the first time in public. In February 2010, Jolie and Pitt sued British tabloid News of the World for reporting that they were separating; the privacy claim was settled the following July for an undisclosed amount, which was subsequently donated to the Jolie-Pitt Foundation.