Elsewhere, the Syrian Observatory for Human Rights said at least 11 regime forces were killed when rebels detonated explosives under a building in the Old City of Aleppo.
"The operation allowed the evacuation of 11 civilians from Bustan al-Diwan and Al-Hamidiya," Governor Talal Barazi told AFP, but it was halted because of "obstruction by armed men who opened fire at the crossing."
Barazi did not identify the gunmen, but "armed men" is a common regime term for rebels fighting to oust President Bashar al-Assad.
Barazi earlier told state TV that most of those evacuated were women, children and the elderly.
Also Read
The United Nations and Syria's Red Crescent began operations to evacuate trapped civilians and deliver aid inside besieged parts of Homs on February 7.
The operation has allowed out some 1,400 of the estimated 3,000 people trapped in Homs for more than 18 months by a government siege that forced residents to survive on little more than olives and wild plants.
The work was made possible by a ceasefire that was extended twice, but expired on Saturday night.
The chaotic UN and Red Crescent evacuation process saw aid convoys come under fire. Shelling killed more than a dozen people despite the nominal truce, with the warring sides trading blame for the violations.
Following their evacuation, around 400 men and boys aged 15-55 were detained by authorities for investigation, raising concern among UN and Red Cross officials.
Barazi said Saturday that 390 male evacuees had left Homs, with 211 released so far.