The couple, who married in August 2014, haven’t been seen together since November 2015.
Angelina, 41, and Brad, 52, attended the premiere of “By The Sea,” a film directed by Angelina.
In their last public appearance together, the pair laughed and joked on the red carpet in Los Angeles.
They were photographed looking happy, with Angelina placing a hand on Brad’s chest as they posed for pictures.
Clad in a strapless gown, the humanitarian and Oscar-winning actress chuckled as she embraced her husband.
Brad stood by his wife’s side at the premiere of her film, clasping her hand during the opening night gala.
The movie, featuring Angelina in both acting and directing roles alongside her husband, depicts the struggles of a discontented married couple.
Reflecting on the film, Angelina admitted it posed challenges during production.
“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.”
She added: “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 that again though.”
The shocking news of their divorce was confirmed by Angelina’s lawyer, who said legal documents were filed on Monday citing irreconcilable differences.
Despite not being photographed together since the premiere, the date of separation is listed as September 15 2016.
TMZ reported that the Tomb Raider actress is asking for physical custody of their six children.
She reportedly asked a judge to give the Fight Club actor visitation, rather than joint custody.
The pair share three biological children, as well as three adopted children together.