Jolie arrived in Libya on Tuesday and toured destruction in Misrata, the city captured by rebels over several weeks of heavy fighting as they pushed to depose Libyan leader Muammar Gaddafi earlier this year.
Speaking in the lobby of a hotel in the city, she praised the "extraordinary" participation of ordinary Libyans both in the rebel army and transitional authorities, as they sought to forge a new nation.
"What's extraordinary ... is that a lot of the people who are part of the solution and are working in positions of even military, and you find that just before the revolution they had retired, or were running restaurants or were selling baby clothes and they've all quit their jobs and they are all working here now on behalf of their country," Jolie told Reuters.
"They have all lost family members ... they've suffered casualties themselves, they've lost limbs themselves and yet they're all really fighting for something they believe in, and for the future of the country for their children, so it's quite moving," she added.
Jolie set off in a sport utility vehicle, accompanied by armed bodyguards, to drive to Tripoli.
She said she had met Libyan transitional government officials during her two-day visit, and highlighted the many needs Libyans faced as they sought to rebuild society and institutions.
"This country is going through so much. It's in transition on so many levels ... It's not just food, it's not just sanitary conditions or the new laws that need to be put into place. It's all of these things at once," she said.
She said her visit sought to highlight the plight of foreign migrants and Libyans who had been displaced internally by the war.
"I'm also here on behalf of the Libyan people to show them solidarity. I think this revolution on behalf of human rights, which is what I feel these people really have been doing and what they have pushed for, and to help them to implement these new laws and help them with the future of their country."
Jolie visited Libyan refugees in Malta and on the Italian island of Lampedusa in June, and went to Tunisia in April to appeal for international support for people fleeing the revolution there.
Jolie is an ambassador for the United Nations refugee agency UNHCR and is expected to announce an expanded role soon. (Editing by Giles Elgood)