It was unclear if the volunteers were taken through territory controlled by Israel on their way from Syria to Jordan.
The White Helmets is a network of first responders who have helped people wounded in Syrian government air strikes, shelling or explosions on rebel territory.
It was formed in the third year of the Syrian civil war and more than 200 of its volunteers have been killed since.
Britain, along with Canada and Germany, will be among the countries settling them on a permanent basis within three months.
“The White Helmets have saved over 115,000 lives during the Syrian conflict, at great risk to their own,” Foreign Secretary Jeremy Hunt and International Development Secretary Penny Mordaunt said in a joint statement on Sunday.
“Many White Helmets volunteers have also been killed while doing their work – trying to rescue civilians trapped in bombarded buildings or providing first aid to injured civilians.
“White Helmets have been the target of attacks and, due to their high profile, we judged that, in these particular circumstances, the volunteers required immediate protection.
“We therefore took steps with the aim of affording that protection to as many of the volunteers and their families as possible.”
Raed Saleh, the head of the White Helmets, told AFP they had been encircled in the provinces of Deraa and Quneitra before their rescue.
