It is estimated that 20,000 pensioners die each winter from trying to cut back on heating costs, according to E.ON.
The firm will identify customers aged 70 or over, on benefits and who are seen to be using less energy than expected for the scheme, which will offer a range of free services, including a hypothermia thermometer.
Jean Fiddes, social manager at E.ON, said the energy firm has a "responsibility to help those most in need".
She added: "We are committed to protecting our older vulnerable customers and as the temperature drops this is more important than ever.
"By reaching out to 10,000 of our customers most at risk we can make a very real difference."
E.ON recently announced it was reducing electricity bills for its consumers not attached to the mains gas in the areas of the east midlands, east of England and the north-west.
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