Jolie Pitt, 41, filed on Monday, citing irreconcilable differences and requesting physical custody of the couple's six children, according to the document obtained by ABC News.
Pitt released a statement to People magazine on Tuesday afternoon that read, "I am very saddened by this, but what matters most now is the well-being of our kids."
The duo, who became a couple in the mid-2000s, have six children: Maddox, Pax, Zahara, Shiloh, Vivienne and Knox. The pair tied the knot in 2014 after almost a decade together.
Pitt continued, "I kindly ask the press to give them the space they deserve during this challenging time."
This statement from Pitt, 52, came after Jolie Pitt's attorney told ABC News, "This decision was made for the health of the family. She will not be commenting at this time and asks that the family be given their privacy during this difficult time."
ABC News' Carolyn Durand and Alyssa Pone contributed to this report.