The operation to evacuate the 50,000 civilians and rebels left in the war-torn city of Aleppo could take days, the Red Cross has said.
Thousands left the besieged city on Thursday under a deal that will allow Syria's regime to take full control of Aleppo after years of fighting.
The Russian Defence Ministry said nine convoys carrying 6,400 people had left the city in the first 24 hours of the evacuation, including 3,000 rebels and 301 wounded.
All buses and ambulances were escorted by the Russian Centre for Reconciliation and members of the Red Cross, the ministry added.
Turkey put the figure of evacuees at 8,000.
UN envoy Staffan de Mistura said about 50,000 people were still trapped, including 40,000 civilians.
The withdrawal began about a month after President Bashar al Assad's forces launched a major Russian-backed offensive to retake all of Aleppo.
In a video message, President Assad said the "liberation" of Aleppo was "history in the making".
US Secretary of State John Kerry said what had already happened in the city was "unconscionable", but warned over the fate of "tens of thousands of lives that are now concentrated into a very small area of Aleppo".
Four Syrian organisations have sent a UN commission a list of 304 attacks in Aleppo where they say Russia bears a "high likelihood" of responsibility for violating international humanitarian law.
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Their letter to the Independent International Commission of Inquiry on Syria, obtained by the Associated Press news agency, said the attacks led to 1,207 civilian deaths, including 380 children.
It said "evidence clearly indicates that Russia has committed or been complicit in war crimes in Syria".
The evacuations were announced on Thursday, after an initial plan for civilians and fighters to leave rebel-held areas collapsed the previous day amid renewed clashes.
The UN Security Council will meet on Friday evening to discuss the crisis in response to a request by France, which is calling for international observers to be sent to monitor the situation and ensure aid deliveries.
European Union leaders also tried to put pressure on Russia, urging the Kremlin to protect civilians, but EU President Donald Tusk acknowledged the bloc was largely powerless.
"We know we are not effective enough. Unfortunately I know who is effective enough, not in humanitarian assistance but in bombing," Mr Tusk said.
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