The Fight Club star released a statement to People, saying that his focus is on the six children he shares with his estranged wife.
"I am very saddened by this, but what matters most now is the wellbeing of our kids," he said in the statement. "I kindly ask the press to give them the space they deserve during this challenging time."
Angelina's lawyer confirmed the shocking split on Tuesday (Sept. 20), saying that the actress had filed for "dissolution of marriage" the day before. Robert Offer added that the "decision was made for the health of the family".
He said: "She will not be commenting, and asks that the family be given its privacy at this time."
According to court documents obtained by TMZ, Angelina asked for physical custody of the couple's six children – Maddox, Pax, Zahara, Shiloh, Vivienne, and Knox.
She has requested joint legal custody and not physical custody, and has asked a judge to grant Brad visitation. Angelina is reportedly not asking for spousal support.
The documents also state that the couple have been separated since Sept. 15.
Brad and Angelina married in August 2014 in a wedding covered by Hello! magazine. The couple, who met on the set of Mr & Mrs Smith, have been together since 2004.
The news came as a shock to the couple's fans and close friends. Last month Brad and Angelina quietly celebrated their wedding anniversary with an intimate evening at the Beverly Hills Hotel in Los Angeles.
A source also told People: "The divorce is a complete shock. They have definitely spent more time apart this year, but it's still a shock. They just celebrated their wedding anniversary together."