Jolie, 41, filed for divorce from Pitt, 52, citing irreconcilable differences on Monday.
Her lawyer, Robert Offer, said the decision had been made “for the health of the family”.
It was Pitt’s second marriage, having previously wed Friends star Jennifer Aniston, and Jolie’s third after actors Billy Bob Thornton and Jonny Lee Miller.
Singer Adele is among those to comment on the split, dedicating a concert in New York on Tuesday to the Hollywood couple.
The 28-year-old told an audience at Madison Square Garden she had been “shocked” by the news and that it felt “like the end of an era”.
George Clooney, who worked with Pitt on Ocean’s Eleven and its sequels, expressed surprise when asked about the matter.
“I feel very sorry to hear that,” he told reporters at a United Nations event. “It’s an unfortunate story about a family.”
Billy Bob Thornton, however, made no comment at a Hollywood event honouring actress Kathy Bates on Tuesday.