Jolie and Pitt flew to Haiti from the neighboring Dominican Republic, where she is filming the movie "The Good Shepherd," directed by Robert De Niro.
The couple, who recently announced that they are expecting a baby this summer, were to get a firsthand look at projects run by Yele Haiti, the charity of Haitian-born hip-hop musician Wyclef Jean.
They were expected to distribute food and toys to boys at a juvenile prison and to visit a school where Yele Haiti gives children the opportunity to play sports.
Pitt, 42, and Jolie, 30, also intended to meet with workers from Yele Haiti's Project Clean Streets, which helps clear litter from the capital of Port-au-Prince.
Jolie, a goodwill ambassador for the U.N., has helped raise money in the past for the charity, which distributes scholarships and food in the Western Hemisphere's poorest country.
The visit comes at a tumultuous time for Haiti, with the country struggling to organize its first elections since former President Jean-Bertrand Aristide was forced from power in a violent rebellion nearly two years ago.