The 41-year-old star, who filed the legal documents on Monday, has cited irreconcilable differences as the cause of the split, reported TMZ.
She has asked for the physical custody of the couple's six children and wants Pitt, 52, to have visitation. Jolie is apparently in favour of a joint legal custody.
Sources close to the couple say Jolie's decision has to do with the way Pitt was parenting the children and she was extremely upset with his methods.
Jolie is reportedly not asking for spousal support. She has listed the date of separation as September 15, 2016.
The news comes as a heartbreak for the couple's fans and shippers but definitely not a shock because the rumours of problems between the two had been there for past few months.
Earlier this year, Hollywood's other famous couples like Johnny Depp-Amber Rose, Taylor Swift-Calvin Harris, Taylor Swift-Tom Hiddleston, Demi Lovato-Wilmer Valderrama and Ozzy Osbourne-Sharon Osbourne announced their splits.
One of the most celebrated Hollywood couples, Jolie-Pitt tied the knot in August 2014 after 10 years of togetherness. Ironically, Jolie directed and starred opposite Pitt in 2015 relationship drama "By The Sea", which was about a couple's attempts to save their marriage.
In fact, Jolie even admitted in an interview earlier this year that filming "By The Sea" nearly destroyed her marriage. "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," she had said referring to the film.
Before Pitt, Jolie had two divorces -- actor Jonny Lee Miller, in 1999 after three years of marriage, and actor Billy Bob Thornton, in 2002 after two years as husband and wife. While, this was the second marriage for Pitt, who was earlier married to former "Friends" star Jennifer Aniston for five years till 2005.