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Actress Joanna Lumley was the first to pledge to help elderly friends and neighbours through the winter by signing up to an NHS scheme.
Lumley said she was "proud" to become a "Winter Friend" and urged others to join the scheme.
She said: "A little help really does go a long way. You will also find, I'm sure, that giving a bit of your time in this way is hugely rewarding.
"Older people can be physically frail but they have a lifetime's wisdom and experience to share."
Former Olympic champion Sally Gunnell, actor Sir Tony Robinson and rapper Plan B are also backing the initiative, an NHS England spokesman said.
Health officials want to recruit an army of good samaritans to care for their elderly neighbours or friends this winter.
NHS England hopes 100,000 people will sign a pledge promising to look in on the elderly as the nights turn colder.
The scheme comes as a sharp rise in excess winter deaths was exposed, with pensioners the worst effected.
Figures released yesterday by the Office of National Statistics showed excess winter deaths rose by 29%, with over-75s accounting for 25,600 out of the 31,000 additional deaths.