The evacuation was agreed as part of a deal that will, in exchange, see the safe passage of scores of civilians from two government-supporting villages that are surrounded by rebels in northern Syria.
The agreement is another example of limited ground-level deals to end fighting in specific areas in Syria.
Buses and ambulances ferried rebel fighters from besieged towns to the Turkish and Lebanese border.
“Initiatives like this one bring relief to besieged or isolated communities and have great value”, Mistura said.
More than 250,000 people have died in Syria since the beginning of the civil war almost 5 years ago.
Previously, the rebels wanted Syrian authorities to halt a broad offensive on rebel-held Zabadani and Madaya towns, while the Iranians and Syrian governments wanted jihadi groups in northwestern province of Idlib to stop their attacks on Shiite towns, which have been subject to repetitive attacks and suffocating siege.
Meanwhile, twin suicide bombs hit Homs on Monday, killing at least 19 people.
Footage aired on state TV showed widespread destruction in the area as firefighters tried to extinguish the blaze. Barrazi said the attacks came in response to the reconciliation deal in the city.
The Britain-based Syrian Observatory for Human Rights said the blasts killed 32 and wounded 90.
The foreign ministers of South Korea and Japan say they’ve reached a deal meant to resolve a decades-long impasse over Korean women forced into Japanese military-run brothels during World War II.
More than 200 wounded Syrian rebel fighters and civilians reached Lebanon Monday en route to Turkey via the Beirut airport, in the second phase of a UN-backed agreement between combatants in Syria’s almost five-year-old conflict.
At the same time, some 126 people from the rebel stronghold of Zabadani near the Lebanese border, which is surrounded by government forces, were evacuated to Beirut for transfer to Turkey.
The Shi’ite Syrians are holed up in an areas mostly under Sunni rebel control and would be able to get to Lebanon where Hezbollah would be able to watch over them, added the sources.
Airport officials said the plane will return to Turkey while another plane takes the Shiite villagers from Turkey to Lebanon later on Monday. The Observatory said the evacuation also began in Foua and Kfarya.