Six hundred people - mostly women, children and the elderly - have been evacuated from the Syrian city of Homs, according to non-governmental organisations.
They were brought out by humanitarian assistance teams on Sunday despite mortar attacks and shooting.
More civilians may be rescued as rebels and the Bashar al-Assad government have extended the ceasefire for another three days.
The evacuation of about 600 of the 3,000 trapped people came as representatives from both sides converged on Geneva, Switzerland, for new peace talks.
In-depth coverage of escalating violence across Syria
Sunday's evacuation was the second after 83 people were brought out on Friday - the first day of the truce.
The Syrian Red Crescent said on Facebook "around 600 people evacuated today, registration is still ongoing. We managed to get 60 food parcels & 1500Kg of flour inside old city".
The Britain-based Syrian Observatory for Human Rights said 611 were brought out - "210 women, 180 children, 91 men over 55 years old and 130 young men who surrendered to Syrian authorities under UN supervision".
It said the men "will be released soon".
Television footage showed women, children and elderly men getting off the evacuation buses.
They appeared visibly exhausted and frail, in a video broadcast by the Beirut-based Al-Mayadeen TV channel.
Homs, much of which has been reduced to rubble, was dubbed "the capital of the revolution" by activists before an offensive in 2012 by regime forces recaptured much of the city.
The civilians evacuated from Homs on Sunday were aided by UN staff and Syrian Red Crescent volunteers amid a strong Syrian army presence.
State television said the operation took place under fire from "armed terrorist groups" - regime terminology for rebels.
But the Syrian Observatory echoed claims by activists that at least five people were killed in shelling that targeted the besieged Homs district of Qarabis.
Activists accused pro-government fighters in neighbourhoods bordering the besieged districts who opposed the truce, of firing the mortar rounds.
Shelling also targeted a Homs aid convoy on Saturday in an attack that killed five residents and wounded 20 others, the Syrian Observatory said.
Elsewhere in Syria, at least 25 members of Assad's Alawite sect were killed by fighters in the Maan area of Hama province, the Syrian Observatory said on Sunday.
It said most of the dead were pro-regime fighters, but state television reported a "massacre" of 10 women.
And in the Palestinian camp of Yarmouk in southern Damascus, besieged since last June, a man and a woman died of malnutrition, it said.
Since the blockade began, up to 80 people have died because of food and medical shortages, the Syrian Observatory estimates.
In yet another development, a group of nuns from the historic Christian-majority Syrian town of Maaloula have appeared in a video aired by Al Jazeera.
The women are reportedly 12 nuns from a Greek Orthodox convent of Mar Takla in Maaloula who were seized by armed men in early December.
The video was recorded on February 5.
On the diplomatic front, the government delegation and members of the opposition National Coalition arrived for the second round of Geneva 2, sources close to the delegations told AFP news agency.
Walid Muallem, the Syrian foreign minister, again heads the government delegation.
It was not yet clear if Ahmed al-Jarba, the National Coalition head, will be in the opposition delegation.
Lakhdar Brahimi, the UN-Arab League envoy, is scheduled to hold separate sessions on Monday, with the opposition in the morning and the regime delegation in the afternoon.
It will then be decided whether to hold a joint session on Tuesday or not, an AFP journalist said.
The warring sides seem far from compromise, however.
While the regime insists that the talks focus on fighting "terrorism", the opposition demands the priority be agreement on a transition that excludes Assad.
The nearly three-year civil conflict in Syria has killed about 136,000 people and displaced millions more.