The Oscar winner disclosed that detail during a recent interview, explaining that prior to adopting her first child -- son Maddox -- from a Cambodian orphanage in 2002, she never had a maternal hankering.
"It's strange, I never wanted to have a baby," the 40-year-old told the Associated Press. "I never wanted to be pregnant. I never babysat. I never thought of myself as a mother."
Growing up in L.A., the daughter of actors Jon Voight and the late Marcheline Bertrand felt "a real emptiness," she said.
She said her feelings changed after filming "Lara Croft: Tomb Raider" in Cambodia in 2000. While there, the actress educated herself about the war-ravaged country and its people.
"I realized there was so much about history that I had not been taught in school, and so much about life that I needed to understand, and I was very humbled by it," Jolie said.
"That trip triggered my realization of how little I knew and the beginning of my search for that knowledge."
After that, she contacted the U.N. High Commissioner for Refugees, then joined the organization in 2001 as a goodwill ambassador. Her parenting epiphany came while she was playing with kids at a local school on a later trip.
"It was suddenly very clear to me that my son was in the country, somewhere," she said.
She has since applied her humanitarian reach to other countries too, and along the way has adopted daughter Zahara, now 11, from Ethiopia, and son Pax, now 12, from Vietnam with then-partner Brad Pitt. The couple went on to have three biological children -- daughter Shiloh, 9, and twins Vivienne and Knox, 7 — before marrying in August 2014. In 2012, the "By the Sea" director and star became a U.N. special envoy.
The "Unbroken" director is now back in Maddox's home country to co-direct "First They Killed My Father," a Netflix film adaptation of Loung Ung's memoir chronicling the Khmer Rouge's 1970s holocaust from the perspective of a young boy.
Maddox, who was only 7 months old when he was adopted and is now 14, is helping with research and preparation for the film.
Follow me on Twitter @NardineSaad