Rescue workers known as the White Helmets are expected to be resettled in Britain after an evacuation from Syria’s conflict-scarred southern border.
Foreign Secretary Jeremy Hunt said in a joint statement with the international development secretary the “brave and selfless” volunteers required “immediate protection”.
The UK had backed an international effort to rescue members of the group and their families from the frontier with the Israeli-occupied Golan Heights.
- Video report by ITV News Correspondent Ronke Phillips
Israel has successfully evacuated 800 White Helmet volunteers and their families from Syria and moved them to neighbouring Jordan on the request of the UK and other nations.
The group was evacuated from the Golan Heights as Syria's Russian-backed government forces closed in.
It marked the first such Israeli intervention in Syria’s civil war, now in its eighth year.
Mr Hunt earlier praised the operation on Sunday as "fantastic".
The regime considers the White Helmets a “terrorist” organisation because it works in areas controlled by its opponents. They are often targeted during attacks.
Jordan has agreed to temporarily house the 422 evacuees, but its Foreign Ministry said Britain, Germany and Canada had pledged to resettle them.
A Jordanian military spokesperson confirmed the details, saying: "The request was approved based on pure humanitarian reasons."
Mr Hunt and Penny Mordaunt released this joint statement:
The Israeli military said its actions did not reflect a change to Israel’s non-intervention policy in Syria’s war, where all the warring parties are considered hostile.
US officials had said they were finalising plans to evacuate several hundred Syrian civil defence workers and their families from south-west Syria as Russian-backed government forces closed in on the Quneitra province.
The officials said The White Helmets, who have enjoyed backing from the United States and other Western nations for years, were likely to be targeted by Syrian forces as they took control of the south-west. Evacuation plans were accelerated after last week’s Nato summit in Brussels.
Since the Syrian government offensive began in June, the area along the frontier with the Golan Heights has been the safest in the south-western region, attracting hundreds of displaced people because it is along the disengagement line with Israel demarcated in 1974 after a war.
The Syrian government is unlikely to fire there or carry out air strikes for fear of an Israeli response.
The White Helmets have typically operated in opposition-held areas across Syria, places where government services are almost non-existent, voluntarily risking their lives to save hundreds of civilians during government air strikes and bombardments.
Over the last month, Syrian government forces aided by Russian air power have swept through south-western Syria to consolidate government control over this strategic corner of the country that straddles the border with Jordan and the frontier with Israeli-occupied Golan Heights.
With its new advances, government forces are, for the first time since the civil war began in 2011, retaking this territory from the rebels and restoring their positions along the disengagement line on the frontier with Israel that is part of a ceasefire agreement reached in 1974 between the two countries formally still at war.