A refugee family is living in a cottage in the grounds of Lambeth Palace.
The historic London residence of the Archbishop of Canterbury is the first sponsor approved under a new scheme announced on Tuesday.
It will see churches, charities, faith groups and businesses provide housing and support for those brought to Britain from Syria and other countries in the Middle East and North Africa under resettlement programmes.
Organisations will provide housing for refugees and help them integrate into life in the UK, gain access to medical and social services and arrange English language lessons.
Launching the Full Community Sponsorship scheme at Lambeth Palace, Home Secretary Amber Rudd said she had the met the family - which includes children aged four to 10.
The youngsters told her they all wanted to be doctors when they grow up.
Ms Rudd said: "The response of the British public to the refugee crisis has been one of overwhelming generosity and many have been moved to make kind offers of assistance.
"This is a ground-breaking new development for resettlement in the UK and I wholeheartedly encourage organisations that can help to offer their support.
"I hope that this new approach will help bring communities together and support these often traumatised and vulnerable families as they rebuild their lives, and contribute to and thrive in our country."
The Archbishop of Canterbury Justin Welby said: "Refugees, like all people, are treasured human beings, made in the image of God, who deserve safety, freedom and the opportunity to flourish.
"It is an enormous privilege to welcome a family to live in a cottage in the grounds of Lambeth Palace."
The scheme is based on a successful Canadian model which reportedly has more communities offering to sponsor refugees than actual refugees.
Individuals and groups take responsibility for families for a year, finding them a home and education.
The Home Office said sponsoring organisations wishing to apply must have status as either a registered charity or "community interest company", the consent of the local authority in which they wish to operate and a "comprehensive plan" for resettlement.
All resettled refugees will have been through a thorough security vetting process.
In September 2015 the Government pledged to resettle 20,000 Syrian refugees. The latest published statistics show that more than 1,800 Syrians have so far been provided with refuge in the UK.
More than 160 local authorities have signed up to accept refugees via the scheme, on a voluntary basis.
In addition ministers also committed to accepting up to 3,000 vulnerable children and family members directly from the Middle East and North Africa.