The ‘Fight Club’ star said he was “very saddened” that the relationship was coming to an end after 12 years together, and just two years of marriage.
He said: “I am very saddened by this but what matters most now is the well-being of our kids.
“I kindly ask the press to give them the space they deserve during this challenging time.”
Angelina’s lawyer, Robert Offer, issued a statement on Tuesday (20 September) saying that her decision had been made “for the health of the family”.
The 41-year-old actress cited ‘irreconcilable differences’ with her husband on divorce papers, which listed their date of separation as 15 September.
The nature of the couple’s differences has not been revealed but TMZ reports there was conflict over Pitt’s style of parenting, with a source saying Jolie was “extremely upset with his methods”.
The couple have six children - Maddox, 15, Pax, 12, Zahara, 11, Shiloh, 10, and eight-year-old twins Knox and Vivienne.
Angelina is seeking custody of all of them, with visitation rights for their father.
Laura Wasser also represented Angelina when she divorced ex-husband Billy Bob Thornton in 2003.