Robert Offer confirmed the news, saying that Angelina filed for "dissolution of marriage" on Monday, adding that the "decision was made for the health of the family".
"She will not be commenting, and asks that the family be given its privacy at this time," the lawyer added.
In a statement released to People, Brad said his main priority is their children. "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."
According to TMZ, the actress is asking for physical custody of their six children. 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 couple married in August 2014 in a wedding covered by HELLO! magazine. Angelina and Brad, who met on the set of Mr & Mrs Smith, have been together since 2004.
The news will have come as a shock to the couple's fans. Last month Brad and Angelina quietly celebrated their wedding anniversary with an intimate evening at the Beverly Hills Hotel in Los Angeles.
This will be Angelina's third divorce. She has previously ended her marriages to Billy Bob Thornton and Jonny Lee Miller.
Brad was married to Jennifer Aniston for five years. The couple split in 2005.
Angelina and Brad welcomed their first child Shiloh the following year in 2006. Two years later the actress gave birth to twins Knox and Vivienne. Angelina is also the proud mum to Maddox, Pax and Zahara, whom Brad adopted when he married the Maleficent star.