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Named Fresh Start, the three-year campaign aims to educate the public about the dangerous effects of secondhand smoke on children in confined spaces such as motor vehicles.
Chief medical officer for Wales Dr Tony Jewell said: "Exposure to these chemicals puts children at risk from a range of conditions, including sudden infant death syndrome and asthma.
"There is robust evidence that the level of toxic chemicals is very high in cars, even with a window open. The Fresh Start Wales campaign aims to make people aware that smoking in cars is dangerous for their passengers, particularly children."
And if the campaign is unsuccessful then an outright ban will be considered.
Welsh First Minister Carwyn Jones said: "A ban on smoking in cars carrying children will be considered later in this five-year term of government if smoking levels do not reduce as a result of the campaign.
Simon Clark from tobacco lobby group Forest was in favour of the campaign, saying: "I disagree that they're poisoning children but I support the campaign.
"I think it's important to encourage parents not to smoke in a car where small children are present out of consideration for the child if nothing else."
But he said he was opposed to a ban, continuing: "We think that would be a step too far and totally unnecessary.
"And I think it's outrageous at the way they're treating smokers considering there are 10m smokers throughout the United Kingdom who contribute a massive amount to tobacco taxation - over £10bn a year."
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