The 'Maleficent' star reportedly submitted papers to end the couple's two-year marriage on Monday (19.09.16), citing irreconcilable differences for their split.
According to TMZ, Angelina is seeking physical custody of their six children, Maddox, 15, Pax, 12, Zahara, 11, Shiloh, 10, and twins Knox and Vivienne, eight, but wants a judge to give the 52-year-old actor visitation rights.
TMZ reported that the 41-year-old beauty decided to end their marriage because she was "extremely upset" with the way the 'Moneyball' star has been parenting the kids and so decided to seek joint legal custody, but not joint physical custody.
The actress-turned-director is not seeking spousal support.
She is being represented by Laura Wasser, who recently represented Johnny Depp in his split from Amber Heard.
The documents state the couple's date of separation as September 15 2016.
They married in 2014 after 10 years together.
After meeting on the set of 'Mr. and Mrs. Smith', Angelina and Brad reunited on screen last year in 'By the Sea' and the actress - who also directed the film - previously admitted working on a film about a rowing married couple just weeks after they tied the knot was "dangerous" for their own relationship.
She said: "It was our way of testing ourselves. We knew that if we could get through this, we'd come out even stronger and happier. And we did.
"We've always liked putting ourselves through challenges, even though it was maybe a little more dangerous for us as a couple. I don't think we want to go through it again though."
Prior to getting together, Brad was married to Jennifer Aniston, while Angelina was previously wed to Billy Bob Thornton and Jonny Lee Miller.