"The buses of rebels have begun moving," said Hassan Ghandour, a member of the local committee overseeing the deal in Moadamiyat al-Sham.
He said the buses held rebels as well as their family members and would head to Idlib province, northwest of Damascus.
Moadamiyet al-Sham has been under a devastating government siege since early 2013.
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Syria's government has championed such local deals -- which typically see rebels evacuated in exchange for an end to their encirclement -- as a way to bring stability to the war-ravaged country.
Another member of the local reconciliation committee who spoke to AFP on condition of anonymity said the evacuees -- rebels and civilians -- numbered 2,100 people.
Any remaining rebels would hand themselves in to Syrian authorities "to have their status regularised," the member said.
"Then, the Syrian army will enter the town and state institutions will return to it. Infrastructure like water and electricity networks will be repaired beginning on Sunday," the member added.
More than 300,000 people have been killed since Syria's conflict erupted in March 2011.