Jolie, 31, gave birth to daughter Shiloh Nouvel Jolie-Pitt in Namibia last month. The couple have two older children, 16-month-old Zahara, adopted from Ethiopia, and 4-year-old Maddox, adopted from Cambodia.
Both Maddox and Zahara's surnames have been legally changed to Jolie-Pitt after Pitt, 42, announced his intention to adopt the children.
The Jolie interview will air Tuesday as part of CNN's entire day of programming devoted to World Refugee Day.
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