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A Downing Street spokesperson said talks with Syrian rebel military leaders will help the UK "better understand the actual situation".
The spokesperson said:
The comments came after the Prime Minister visited Jordan's border with Syria.
Foreign Secretary William Hague announced the UK is opening talks with Syrian rebel military leaders in a bid to unite the opposition and end the bloodshed.
Mr Hague said in a written statement to Parliament that he has given the green light to his special envoy to the opposition, John Wilkes, to arrange meetings to initiate discussions.
"All contacts will take place outside Syria, and then only in environments we deem suitably secure", Mr Hague wrote. "Through continuous assessment, we will make every effort to ensure that FCO officials engage only with legitimate representatives of the opposition".
"The decision to engage with military representatives of the armed opposition in a political dialogue supports our efforts to achieve a peaceful and sustained political solution to the crisis", he added.
Mr Hague's comments came as Prime Minister David Cameron met refugees from the conflict at a UNHCR camp in Jordan.
Prime Minister David Cameron pledged to increase humanitarian aid by £14 million as he visited a UNHCR camp for Syrian refugees in Jordan, Reuters reported.
Mr Cameron was accompanied by Jordanian Foreign Minister Nasser Judeh as he met UNHCR officials at the camp, based in an area where approximately 500 refugees cross the border from Syria every day.
UNHCR representative Andrew Harper said the conditions at the camp are improving.
Mr Harper said, "Five hundred plus came last night and we know that the refugees in Jordan are actually talking to their friends and relatives in Syria and saying 'look, that the situation is improving in the camp, come over'".
Prime Minister David Cameron said he would like Syrian President Bashar al Assad to face "full international justice for the appalling crimes that he has meted out on his people".
David Cameron has thanked the Jordanian Armed Forces for helping Syrians fleeing Assad's brutality, British Ambassador in Jordan Peter Millett has said.
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Prime Minister David Cameron said Syria's President Bashar al Assad should face "full international justice" for his "appalling crimes".