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 tomorrow.
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.
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.
"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.
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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