Some 300 Syrians have fled Homs after both sides agreed to extend a three-day truce in the Old City, which has been under siege for 18 months.
The Syrian Red Crescent confirmed the latest evacuations on Twitter.
Hundreds of civilians were allowed to leave at the weekend after the local governor agreed a truce with the UN.
Meanwhile, government and opposition negotiators have resumed peace talks in Geneva. Analysts say that little progress is expected.
The opposition wants the government to commit in writing to the 2012 Geneva Communique, which called for the formation of a transitional administration with full executive authority.
President Bashar al-Assad's government has ruled out any transfer of power.
The first round of talks ended last month with no firm agreements and both sides trading insults.
The second round opened on Monday with preliminary discussions aimed at thrashing out an agenda, but the two sides have not yet met face-to-face.
Syria's civil conflict has claimed more than 100,000 lives since 2011 and has driven 9.5 million people from their homes.
During the first three-day ceasefire in Homs, hundreds of civilians were allowed to leave.
The evacuations took place amid mortar fire and shooting, which both sides blamed on each other. Activists say several people were killed.
Although the situation in Homs was discussed during the first round of talks in Geneva, the truce was actually agreed between Homs governor Talal Barazi and the UN resident co-ordinator in Syria.
Mr Barazi said on Sunday that talks were going on to extend the ceasefire for another three days.
UN aid chief Valerie Amos later confirmed in a statement that the truce had been extended for three days.
French Foreign Minister Laurent Fabius said France and other countries would present a resolution at the UN calling for greater access for humanitarian aid.
"We are asking for stronger action as far as the humanitarian side is concerned, that medicines and food supplies are handed out in cities," he told French radio.
"It is absolutely scandalous that there have been discussions for quite a while and that people are still being starved every day, and so along with a number of other countries we will present a resolution at the UN along those lines."
But China and Russia did not turn up to preliminary discussions on the draft.
Russian diplomats had already dismissed the idea of a so-called humanitarian resolution.
The Syrian government has acknowledged that some of those evacuated from Homs on Sunday were detained after they left.
A Syrian information ministry spokesman told the BBC that 103 "militants" had been detained for security checks, but had since been released.
But other reports suggest the men have not been released, and are still being detained with their families.
In other developments:
- A third shipment of chemical weapons from the government's arsenal has left Syria, the Organisation for the Prohibition of Chemical Weapons said
- Rebel fighters from the hardline Islamist group Jund al-Aqsa have killed at least 21 civilians and 20 pro-government militiamen in Maan, a predominantly Alawite village in Hama province, the UK-based Syrian Observatory for Human Rights (SOHR) has said
- The jihadist Islamic State in Iraq and the Levant (ISIS) is reported to have withdrawn from the eastern province of Deir al-Zour after days of heavy fighting with rival rebel groups