Buses began transporting Syrian rebels and their families Saturday from the last opposition-held neighborhood in the central city of Homs.
So far, nearly 1,500 people have evacuated from al-Waer, most of whom were civilians. Their departure is part of a Russian-backed deal signed earlier this month.
Homs Governor Talal Barazi told AFP 423 rebel fighters had also left the district.
"Not a single weapon or fighter will be left in Waer," he said.
The fighters and their families are being taken to the northern rebel-held town of Jarablus on the border with Turkey.
Officials say the exodus will take several weeks.
The evacuation came about after a deal was struck last week between Syrian government and rebel representatives to allow 100 Russian troops to deploy in al-Waer and oversee the operation.
Thousands more civilians are expected to leave Homs to avoid conscription or arrest by Syrian security forces.
The Syrian Observatory for Human Rights estimates 12,000 will leave under the agreement, including 2,500 rebels.
The Waer neighborhood of Homs is home to 75,000 people.