The 38-year-old actress, who wore a shimmering, embellished black Atelier Versace gown, arrived at the annual event with partner Brad Pitt and their eldest son, 12-year-old Maddox.
Upon accepting her Academy Award, Jolie received a standing ovation from fellow guests and paid tribute to Pitt, her children and her late mother Marcheline Bertrand.
The Oscar-winning star, who was recognised for her role as special envoy for the United Nations Refugee Agency, held back tears as she said to Pitt during her speech: "My love, your support and guidance makes everything I do possible.
"Mad, you and your brothers and sisters are my happiness."
Jolie added: "(My mother) was very clear that nothing would mean anything if I didn't live a life of use to others. To stand here today means I did as she asked. And if she were alive, she'd be very proud."
Other stars at the ceremony included Idris Elba, Naomie Harris, a slimline Jake Gyllenhaal, Matthew McConaughey, Mark Wahlberg, Angela Lansbury and Steve Martin.