Homs activists issued the plea after UN-Arab League envoy Lakhdar Brahimi said the regime had agreed to allow women and children safe passage out of rebel-held areas in the central city.
Brahimi on Sunday also voiced hope that a humanitarian aid convoy would be allowed to enter the besieged areas yesterday but that has not happened yet.
Dubbed "the capital of the revolution," Syria's third city Homs has paid a high price for its opposition to Assad.
"We need the siege lifted and to ensure that residents can enter and exit through safe corridors, without passing through regime checkpoints," the activists said in a statement.
Should the siege remain in place, "all solutions will be futile, and will do nothing to end this tragedy," they added in remarks addressed to opposition representatives taking part in the Geneva peace talks.
"There are dozens of people who need immediate surgery, and more than 250 families are suffering because of the siege."
Yesterday, the International Committee of the Red Cross (ICRC) said there had been "no concrete step taken" to provide aid or evacuate women and children from the besieged districts.
The Syrian Observatory for Human Rights says an estimated 500 women and children are among those trapped in rebel areas which cover just a fraction of Homs city.
Among them is Dutch priest Frans van der Lugt who joined an Internet appeal launched by activists, describing the situation in the neighbourhoods as "intolerable.
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