The campaign was developed in consultation with young people and medical experts and uses the voices of people aged 14 to 24 who have experienced the harms of vaping.
In one ad, a young man explains that vaping meant when he tried to breath deeply.
"It felt like my lungs were squeezing in on themselves," he says.
Usage rates among people aged 16 to 24 has jumped nearly four-fold in recent years, with one in six adolescents vaping in the year to mid-2022.
"It took us over three quarters of a century to reduce smoking among men from around 72 per cent to 14 per cent," Health Minister Ryan Park said.
"We have an opportunity to stem the tide of another emerging public health crisis that could have a lasting impact for generations of young people to come."
The NSW advertisements encourage young people to consider the proven health harms of vaping, such as nicotine addiction, lung damage, breathlessness, nicotine poisoning and burns from exploding vapes.
People wanting to support or advice to quit should talk to their GP, download a quit vaping app or call Quitline.
"Not only are vapes full of harmful chemicals that have been known to cause cancer, there is also growing evidence that non-smokers who vape are more likely to take up smoking, which can significantly increase their cancer risk," Cancer Council NSW chief cancer officer Professor Tracey O'Brien said.
"We are very concerned that a new generation of people will become addicted to smoking if vaping use continues to increase in young people."
The campaign coincides with NSW curriculum resources being updated to better address the dangers of vaping.
An online training module for school staff is also being created to have conversations with students, and webinar resources will soon be available for parents and carers, the government said.
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