The evacuation began on Friday and the national Syrian broadcaster said two busloads were leaving Homs, with a total of 35 people on board.
On Thursday, Homs Governor Talal al-Barazi and UN resident coordinator, Yacoub El Hillo, agreed to secure the exit of women, children and the elderly from the ancient parts of the central city also known as the Old City.
The deal allows the entrance of humanitarian assistance for civilians who choose to stay, while the two sides have also agreed on a pause in fighting while the deal is being carried out.
Syria’s deputy foreign minister earlier said Damascus is happy to provide humanitarian supplies to the needy civilians inside the conflict areas.
Media reports from Syria indicate that the civilians had been held as “human shields” by terrorist groups fighting against the government of President Bashar al-Assad.
UN-Arab League Special Representative for Syria Lakhdar Brahimi had earlier said that Syrian had agreed to allow women and children out of the beleaguered city.
Syria has been gripped by deadly violence since March 2011. Some sources say more than 130,000 people have been killed and millions displaced due to the violence fueled by Western-backed militants.
The Western powers and their regional allies — Qatar, Saudi Arabia and Turkey — are believed to have been supporting the militants operating inside Syria.