The funding, announced by housing minister, Grant Shapps, will be used to provide financial advice, renegotiating rents and where necessary helping people move to more affordable accommodation.
A further £1.5 million has been made available to help improve access to the private rented sector for single homeless people through the voluntary sector across the country.
This funding is on top of measures in the Spending Review designed to help the most vulnerable - including the homeless.
Shapps said: "It is vital to Britain's economic future that we tackle the record Budget deficit that we inherited but we must also ensure that the most vulnerable in our society are protected. That's why in the Spending Review, we have maintained funding where it is needed most.
"That's why we've protected homelessness grant funding, providing over £7 billion to support struggling families and the most vulnerable, helping families avoid repossession, helping take rough sleepers off our streets and helping people live independent lives that couldn't otherwise do so.
"And today, I can confirm an extra £10 million for London councils, so they can support families affected by the housing benefit changes, and an additional £750K to help work towards ensuring no-one spends more than one night sleeping rough."
