The two tied the knot in a private ceremony in August 2014, attended by their six children.
According to TMZ, Angelina began divorce proceedings officially when she filed the papers on Monday (19 September), with the date of their “separation” listed as 15 September.
TMZ has claimed that the Oscar-winning actress is asking the judge for “physical custody” of their children.
According to the site, “no third party” is involved in the alleged split.
Angelina’s lawyer Robert Offer said of the split “[Her] 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.”
Laura Wasser also represented Angelina when she divorced ex-husband Billy Bob Thornton in 2003.
Brad and Angelina famously got together a year later, after meeting on the set of the film ‘Mr And Mrs Smith’.
Their relationship was initially plagued with rumours that Brad had been unfaithful to his then-wife Jennifer Aniston, though Angelina insisted this was not the case.
Over the course of their relationship, Brad became legal parent of Angelina’s adopted children, Maddox and Zahara.
Together, the couple another son, Pax, as well as welcoming daughter Shilouh in 2006, and twins Knox and Vivienne in 2008.
More recently, the two stars appeared alongside each other in ‘By The Sea’, which Angelina co-wrote and directed, telling the story of a married couple who are unhappy in their relationship.