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Mr Khan said he will expand his new Right to Buy-back fund to help councils purchase homes which could be used to resettle families arriving from Afghanistan.
Housing associations are also being encouraged to apply for funding for suitable homes that can be delivered quickly.
Mr Khan said in a statement that he will invite London councils to submit bids to his Right to Buy-back fund, which allows them to buy former council homes back from the private sector, with the programme to have a particular focus on family-sized properties.
The mayor announced the fund last month in a bid to help councils and council-owned housing companies acquire homes that would be let at social rent levels or used as accommodation for homeless families.
“It has been devastating to watch the crisis unfold in Afghanistan and I’m determined to do everything in my power to support those escaping the country,” Mr Khan said.
“London has a proud history of providing sanctuary to those in need and by working together we can help these refugees find a welcoming home in our city.”
Several London boroughs have told the government they want to support those fleeing the brutal Taliban regime in Afghanistan and take in refugees.
Richmond, Camden, Ealing, Hackney, Hammersmith & Fulham, Kingston, Lambeth, Islington and Lewisham are among the London councils to have offered to house Afghan refugees.
Dr Nooralhaq Nasimi, director of the UK’s Afghanistan and Central Asian Association, said: “With the crisis unfolding in Afghanistan many Afghan refugees will be desperately looking for a safe place to call home.
“I am proud that the Mayor of London and London councils are leading the way in welcoming Afghan refugees and taking active steps to help accommodate them when they arrive and seek to build new lives in the city.”
London Councils provided briefing about the government’s new Afghan Citizens’ Resettlement Scheme, modelled on a similar scheme mobilised to house Syrian refugees in the UK.
The government has confirmed plans to resettle 5,000 Afghan nationals who are “at risk due to the current crisis” in its first year.
Priority will be given to women and girls as well as religious and other minorities.
However, in the briefing notes seen by The Standard, London Councils told its local authorities “details of the scheme are still to be confirmed” and there are several outstanding questions to be clarified.
Among the questions, it is seeking clarity on is whether arrivals will be granted permanent leave to remain and the right to work.
Also it looks at claim benefits as well as how far in advance councils will know about family sizes and extra support needed.
It also has asked the government to provide information regarding a timeline for arrivals over the five years.
The Ministry of Defence says the UK has evacuated almost 7,000 Afghan individuals and their families out of Kabul.