"I am very saddened by this, but what matters most now is the wellbeing of our kids," the actor said in a statement to E! News.
"I kindly ask the press to give them the space they deserve during this challenging time," he continued, asking for the pair's six children to be left out of the spotlight as their marriage comes to an end.
Pitt and Jolie who married in Correns, France in 2014 and have been together for over a decade, share 15-year-old Maddox, 12-year-old Pax, 11-year-old Zahara, 10-year-old Shiloh and 8-year-olds Knox and Vivienne.
On Tuesday, news outlets reported that Jolie, 41, filed for divorce from Pitt, 52, citing irreconcilable differences. Jolie is said to not be seeking spousal support and is requesting sole custody of the children with Pitt getting visitation rights and joint legal custody.