"Today a number of people have arrived in the UK as part of the Vulnerable Persons Resettlement scheme," said a Home Office statement.
The government would not give details of how many refugees had arrived, or where in Britain they would be resettled.
Under the expanded scheme, the new arrivals will receive housing, access to medical care and education and will be granted five years' humanitarian protection.
After that period they will be able to apply to stay in Britain.
Britain had accepted 216 Syrian refugees under the scheme before this month's announcement and has granted asylum to almost 5,000 Syrians since the Syrian conflict broke out in 2011 -- far fewer than countries like France, Germany and Sweden.
European Union ministers on Tuesday pushed through a deal to relocate 120,000 refugees, but faced fierce opposition from central and eastern states.