The evacuation of some of 3,000 trapped people who had little more than olives and herbs to eat for more than 600 days came ahead of a new round of peace talks.
The Damascus delegation and members of the opposition began arriving in Switzerland for a new round of the so-called Geneva II peace talks scheduled to begin on Monday.
Today's evacuation from Homs was the second in three days after a UN-brokered truce for besieged districts of Syria's third city began on Friday.
Five men were killed when one besieged district was hit by mortar fire as today's evacuation operation got under way, the Syrian Observatory for Human Rights said.
They were the latest deaths in a nearly three-year conflict that has killed 136,000 people and displaced millions.
"Four hundred and twenty besieged people came out today from the Old City districts of Homs, and the operation is still under way," Homs governor Talal al-Barazi said.
Television footage showed women, children and elderly men getting off the buses that brought them out of the besieged areas.
They appeared visibly exhausted and frail, in video broadcast by Beirut-based channel Al-Mayadeen. Children, carried by their parents, looked pale.
The civilians were aided by UN staff wearing helmets and blue vests, and by Syrian Red Crescent volunteers. There was also a strong Syrian army presence at the evacuation site.
"We had nothing. All the children were sick, we even had nothing to drink," said one exhausted woman, her three children standing round her.
State television said the operation took place under fire from "armed terrorist groups", using regime terminology for the rebels.
But the Britain-based Observatory echoed claims by activists in the besieged areas that at least five people were killed in shelling that targeted the besieged district of Qarabis.
Activists accused pro-regime militiamen positioned in neighbourhoods bordering the besieged districts, who opposed the truce, of firing the mortar rounds.

Shelling also targeted an aid convoy entering the besieged districts yesterday in an attack that killed five residents and wounded 20, the Observatory said.


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