About 6,000 people are expected to volunteer to help run the scheme
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A charity supporting homeless people has called on the government to provide £300m for education to help prepare them for employment.
The call came from the charity Crisis as it opened seven hostels across London for Christmas.
Crisis is providing food, bedding, medical checks, benefits advice and even a dog "creche".
Celebrity chef Jean Christophe Novelli was expected to volunteer to cook but did not turn up for "personal reasons."
It is the 35th year Crisis has organised its Open Christmas scheme which runs until 30 December.
30,000 meals
The project offers internet access, medical care, television, eye-testing, hair-cuts, skills training and advice on housing and benefits.
Crisis estimates that the centres will serve up 30,000 meals over the holiday period.
The French-born Michelin-star chef Mr Novelli was due to help out with the cooking for up to 300 people at the opening of a centre close to Liverpool Street station.
Phil Power, head of communications for Crisis, said it was "disappointing".
"We were just informed that he was very sorry that he couldn't come due to personal reasons," he said.
The charity has said 97% of homeless people in the UK want a job, but 37% have no qualifications, and more than half have been out of work for over three years.
Leslie Morphy, chief executive of Crisis, said: "Learning can literally change lives.
"If the government recognised the importance of learning in tackling homelessness and committed substantial funds, we could help so many more homeless people."
A spokesman for the Department for Communities and Local Government said: "Getting homeless people into training and employment is a key part of the government's strategy for preventing and reducing homelessness.
"We are providing £90m through the Hostel Capital Improvement Programme to make hostels places of change."