The 'World War Z' star was reportedly told about the split only hours before the papers were filed by the 'Maleficent' actress' legal team.
A source told Us Weekly magazine: "Brad only found out about the divorce decision on Monday."
Meanwhile, it was previously claimed that Angelina decided to split from Brad, 52, after an unknown "incident", which happened a week ago.
An insider said: "The final divorce decision was only made one week ago. An incident took place and prompted Angelina to act and file."
However, the pair's relationship is said to have been on the rocks for months.
A pal said: "I could say the divorce announcement is a shock, but it's not. This divorce deal has been brewing for a long time.
"When Angelina underwent her mastectomy in 2013, her health and life in general became a priority for her. Her views on life changed. Suddenly she saw herself walking in her late mother's shoes - and she was no longer that wild, fun loving woman she used to be, she was taking things a lot more seriously.
"Brad was supportive, and wanted to be there for her, so they decided to marry - more for the sake of their six children than themselves. They wanted the kids to have the security of knowing their parents were committed because they had been very affected by their mom's ill health."