In an elegant brown dress with tassel details, the Hollywood star and UN special envoy introduced Malala Yousafzai, 15, to the audience in New York via a video link from the UK.
"Today I'm going to announce the happiest moment of my life" said Malala, shyly covering her face, before revealing a new girls' school will be built in Pakistan thanks to a donation from the Tomb Raider actress.
Angelina committed 200,000 dollars (£130,000) to Malala's Fund for girls' education in Pakistan after admiring the teenager's activism and dedication that caused Taliban attackers to shoot her for her outspokenness in October.
Malala was taken to Britain for treatment, including skull reconstruction, and was released last month to begin schooling in England.
Due her immense bravely, Malala was shortlisted for Time Magazine's Person of the Year in 2012 and recently signed a deal to write her memoir.
"Here's what they accomplished," Angelina said of Malala's attackers. "They shot her at point-blank range in the head - and made her stronger. The brutal attempt to silence her voice made it stronger."
Angelina, a special envoy for the UN refugee agency, said Malala's father told her his daughter came sixth in a poll of the world's most influential people, closely followed by none other than US President Barack Obama.
In a nod to her position in the poll Angelina smiled and concluded "So we can learn a lot from this girl."