Brad Pitt says he is "very saddened" that his wife Angelina Jolie is filing for divorce.
The Hollywood power couple, known collectively as Brangelina, married in 2014 after 10 years together.
Robert Offer, Jolie's lawyer, says the actress filed for the dissolution of the marriage "for the health of the family".
In a statement to People magazine, Pitt said: "I am very saddened by this, but what matters most now is the well-being of our kids.
"I kindly ask the press to give them the space they deserve during this challenging time."
Jolie filed for divorce on Monday citing irreconcilable differences, according to legal documents filed with the Los Angeles Superior Court.
The actress has asked for physical custody of the couple's six children - Maddox, Pax, Zahara, Shiloh, and twins Knox and Vivienne.
She also filed for Pitt to be granted child visitation rights and to share legal custody of the children.
Jolie is being represented by divorce lawyer Laura Wasser, who helped in her divorce from Billy Bob Thornton and has represented Johnny Depp in his divorce from Amber Heard.
Pitt, 52, and Jolie, 41, first met when they played married spies in the film Mr And Mrs Smith, when Pitt was still married to Friends star Jennifer Aniston.
The couple married in private at their chateau in France in 2014.
Their ceremony included all their children, including adopted offspring Maddox, Pax and Zahara and their daughter Shiloh and twins Knox and Vivienne.
Jolie was previously married to Thornton and British actor Jonny Lee Miller.
Since Mr And Mrs Smith, the couple have appeared on screen together in By The Sea, a film written and directed by Jolie and produced by Pitt, in which they played a glamorous couple whose marriage is in crisis.
In May 2013 Jolie had a preventative double mastectomy after tests showed that she carries the BRCA1 cancer gene, and she later told US TV show Today: "I knew through the surgeries that he (Pitt) was on my side and that this wasn't something where I was going to feel less of a woman, because my husband wasn't going to let that happen.
"To face these issues together and speak about them and talk about what it is to be human, I think can be a beautiful thing."
© AAP 2016