Kicking off yesterday, the Department of Health campaign has called on the nation to quit smoking for 28 days in the first ever mass-quit event.
Other stars on board include Joe Swash, Gordon Ramsay and Kyran Bracken.
Using their expert areas - Health, Wealth and Self - the stars will offer top tips and advice for those wanting to quit.
Employers, councils and local stop smoking services will also be supporting the campaign.
Support and encouragement is also offered via a Stoptober Smartphone app, a Facebook page, and Stoptober support pack.
Stoptober mentor and ex-footballer Ian Wright said: "Smoking is detrimental to our health and, not just for the smoker but, for all of those around them too.
"This is a fantastic campaign, which will really help encourage quitters to work together and give up cigarettes for good.
"I will be supporting everyone by showing ways to improve health and fitness for people of all levels, and to make sure the cigarettes stay stubbed out."
Celebrity make-up artist Gary Cockerill added: "Not many people realise how damaging smoking is for skin, hair and teeth.
"It causes premature ageing, yellowing of the teeth and brittle and smelly hair.
"I'll be providing some top insider beauty tips and advice on how to improve 'smoker's skin' and minimise the harmful effects smoking has to our looks."