Most Revd Justin Welby has said there is room for one or two families in a 4-bedroomed cottage at Lambeth Palace.
It was something the archbishop has been considering for "a while", according to Lambeth Palace.
His gesture follows a similar move by the Catholic church after Pope Francis said two refugee families would move into Vatican housing.
Britain is taking 20,000 refugees from the camps on the borders of Syria over the next five years.
A Lambeth spokeswoman said: "As a Christian who leads the Church of England it is something he feels absolutely passionate about.
"As the archbishop has said, Jesus was a refugee, and there are refugees here who are desperate for sanctuary from war-torn places and the archbishop is completely torn about their situation and wants to make a difference."
It's believed the rent for the refugees will be paid for by charitable funds under the archbishop's personal control.
