Aid workers said around 450 people including opposition fighters and civilians left two areas besieged by regime forces on Monday for Turkish and Lebanese border crossings under a UN-brokered deal between the warring sides.
More than 130 people - mostly wounded rebel fighters - left the town of Zabadani, which is located near the Lebanese border.
The UN-backed deal promises safe passage to Turkey via Beirut for the fighters from Ahrar al Sham and other local Syrian rebels who were holding Zabadani for months.
Fighters against the regime launched attacks on two Shiite villages in an area bordering Turkey that is mostly rebel-controlled after a series of advances against the regime army earlier this year.
The United Nations has been trying to broker local ceasefires and self-passage agreements aimed at stopping Syria’s almost five-year civil war which has resulted in the deaths of at least 250,000 people and caused around five million to flee to other countries.
At the beginning of December regime officials announced that they had agreed on a deal with fighters allowing them to withdraw from the last rebel-controlled area of the city of Homs in a local ceasefire deal.
Despite the agreement two major bomb attacks claimed by the DAESH terrorist group took place in the Zahra District of Homs and killed 48 people.
Another deal that aimed to extract more than 2,000 DAESH terrorists from south Damascus was scuttled last week in a blow to the UN's efforts.
Iran, which backs Bashar al Assad, and Turkey, which backs the rebels, helped to organise local ceasefires in Zabadani and two villages in Idlib in September with the first phase overseen by the International Committee of the Red Cross.