The 13 were the last in their camp, an old building designated for people displaced by fighting in Bosnia that ended 16 years ago.
For years, authorities in Rogatica tried to find a permanent solution for them, but it wasn't until after Jolie and her partner Brad Pitt visited last year that the U.S. agreed to donate some $600,000 for housing.
Patrick Moon, the U.S. ambassador to Bosnia, opened the doors of the two-story building Thursday.
Jolie is a goodwill ambassador for the U.N. refugee agency. The refugees in Rogatica are convinced her lobbying aided their cause.