It is hoped tens of thousands of displaced people will benefit from the Homes for Ukraine refugee scheme.
Under the Homes for Ukraine scheme, people in the UK will be able to nominate an individual or family to stay with them rent-free, or in another property, for at least six months.
The first hosts and refugees will be matched this week, allowing the first Ukrainians to arrive in the UK through this route in about two weeks' time, the BBC's chief political correspondent Adam Fleming says. Local authorities will also receive £10,500 in extra funding per refugee for support services - with more for children of school age.
The children's charity said it was "vital child protection is built into every stage of the government's and local authorities' response to this crisis".
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