On Wednesday, buses began leaving the Old City under a deal brokered by the United Nations.
At least three buses have arrived in rebel-held territory to the north, carrying a number of armed fighters.
"Three buses have left, carrying 120 people in total, a mixture of wounded and non-wounded civilians and fighters," Abul Hareth al-Khalidi, a rebel negotiator, said.
Homs’ governor also confirmed the launch of the evacuation.
It marks the end of any militant presence in the heart of the major city once dubbed the capital of the uprising against President Bashar al-Assad.
Reports say the militants were sad and bitter as they failed to win against the government troops after two years in the city.
The government's forces followed a tactic against the militants that some Syrian army officers called "surrender or starve".
The siege of the Old City was tightened in recent months with intense shelling and air strikes.
The deal was brokered by the UN - which is also supervising the buses now heading into the Old City - and was agreed only after many months of negotiation.
The deal reportedly also involves easing a siege of two predominantly Shia Muslim towns in the north loyal to President Assad.
Reports say the armed groups within the Old City were deeply divided about whether to accept a ceasefire.
The al-Nusra Front, which is affiliated to al-Qaeda, wanted to try to break the siege with a series of suicide bombings. It attempted to do this, but failed, and al-Nusra terrorists will be on the evacuation buses too.
One more district of Homs is still holding out, al-Wair on the periphery.
Militants there have accepted a ceasefire and will leave, too, as soon as arrangements are made.
BA/BA