International Development Secretary Justine Greening, said assistance would contribute "to deliver winter clothing to save lives, food and medicines.
Ms Greening visited the Jordan where Syrian refugees arrive in unprecedented numbers.
The additional funding means that the United Kingdom has now provided £89.5 million euros for the Syria.
Friday, a UN official has told the BBC there had been a great leap in the number of Syrian refugees entering the country, which puts considerable pressure on resources.
Some 6,400 Syrians arrived in the main camp in Jordan in the last 24 hours alone, fleeing continued fighting a well as shortages of food and fuel, according to the United Nations.
The United Nations has described the flow of people as "absolutely dramatic".
"Still not enough".In Jordan, Ms Greening said: "my visit today gave me a chance to see first-hand the incredible generosity of Jordanian ordinary mind showed to open their House to strangers in need."
"It's a story repeated in the nearby villages of Syria in the whole of the region, and I welcome the continued efforts of Governments and communities as the host. But we cannot and must not leave them to assume that only answer."
A little less than half of the new British aid funding will go to help Jordan to cope with the influx of people, particularly those who are most vulnerable in winter conditions, said Ms. Greening.It is sent by the agencies, which aims to reach people in the Government and the opposition-controlled areas.
Remaining aid will contribute to medical facilities and to deal with the tens of thousands of injured and sick persons in the Syria. It will also be used to buy vital supplies of bread and flour.
Ms Greening said the United Kingdom and one handful of others had always "shown the way in responding to this crisis", but said the "vast majority still make a pretty".
"This is simply not acceptable and must be changed," she added, calling the international community to "get behind the United Nations and [enable] waves promises into real support".
Refugees in doubleThe United Nations will hold a conference in the Kuwait week next to try to reduce a deficit that is important in promises of help, as the humanitarian cost of the conflict intensifies.
He has warned that the number of Syrian refugees in neighbouring countries could double to 1.1 million by June if the war does not end.
The conflict in Syria began almost two years with demonstrations against the Government of president Bashar al-Assad.
The protests quickly degenerated as opponents of Mr. Assad took up arms to resist a brutal repression by the authorities.
The conflict has left people over 60 000 dead and 2 million displaced.
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