The couple, who officially married in 2014, have six children together.
Citing irreconcilable differences, Jolie is seeking full physical custody of all of the children, according to the court documents filed in Los Angeles County Superior Court. She is also asking that Pitt be granted joint legal custody and visitation rights.
According to TMZ, which first reported the news, Jolie was upset with Pitt's parenting "methods."
"This decision was made for the health of the family. She will not be commenting, and asks that the family be given its privacy at this time," Jolie's attorney, Robert Offer, said in the statement to Reuters.
Pitt asked for privacy in a statement to People, saying he is most concerned with protecting his children.
"I am very saddened by this, but what matters most now is the well being of our kids," he said. "I kindly ask the press to give them the space they deserve during this challenging time."
While speculation over what prompted the divorce ran rampant Tuesday, Joile's father, actor Jon Voight, told BuzzFeed News that "something severe must have happened."
"It’s a shock," he said. "Something must have happened. Something severe must have happened and I’ll definitely find out soon."
"I will hopefully be seeing Angelina and the kids very soon," he added. "Her priority is the children, it has always been. I’m a bit shocked as everyone else."
Reps for both Jolie and Pitt did not return calls to BuzzFeed News.
The superstar couple were famously first linked in 2004, when they co-starred in Mr. & Mrs. Smith. Pitt was still married to Jennifer Aniston at the time.
At the time, tabloids noted their "growing intimacy" but Pitt and Jolie denied a romance, Entertainment Weekly had reported.
Shortly after, in January 2005, Pitt and Aniston announced they were divorcing.
Pitt was soon spotted spending time with Jolie and her young son Maddox. In 2006, the couple announced they were expecting, and daughter Shiloh was born in May.
The couple are also parents to daughter Zahara, son Pax, and twins Vivienne and Knox.