If the application is successful the children's names will be changed to Maddox Jolie-Pitt and Zahara Jolie-Pitt.
Jolie, 30, adopted Maddox from Cambodia and baby Zahara from Ethiopia.
The actors have been linked since Pitt split from ex-wife Jennifer Aniston, but both have refused to speak publicly about their relationship.
The rumours began when they starred together in the film Mr and Mrs Smith and have since been pictured together with the children.
"We are confirming that Brad Pitt is in the process of becoming the adoptive father of both children," said Pitt's publicist Cindy Guagenti.
Pitt, 41, went to Ethiopia with Jolie when she adopted Zahara, who is about 10 months old, in July.
Jolie adopted four-year-old Maddox in 2002 while she was married to actor Billy Bob Thornton. The couple split soon after.
She and Pitt recently travelled to Pakistan to witness the devastation caused by October's earthquake as part of Jolie's work as a United Nations goodwill ambassador.
The Tomb Raider actress appealed for more international aid to be delivered to the country soon before winter strikes and more people are added to the death toll.
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