The funding would comprise $4.3 million to bolster compliance and enforcement on state control laws and $2.5 million on services to help young people quit vaping, the government said on Monday.
"The evidence suggests that vaping is now becoming a gateway for an increase in smoking rates in young people," Premier Chris Minns said in a statement.
"This is a significant public health challenge and taking action on the illegal imports of vapes is going to require cooperation with all levels of government."
NSW health authorities seized 23,247 vapes valued at more than $695,000 in a week-long campaign against illegal vapes earlier this month.
Ongoing work by NSW Health has highlighted the importance of further action on supporting young people addicted to vaping, the government statement said.
"There is strong evidence that non-smokers who use e-cigarettes or vapes, are three times more likely to go on to smoke traditional tobacco cigarettes as people who have never vaped."
"For young people, nicotine can cause changes to brain development, impaired learning and memory, and may worsen stress, depression and anxiety."
The commitment comes after the federal government in May announced a $234 million boost for tougher regulation of vapes, including new controls on their importation and packaging amid community concern over e-cigarettes.
In NSW, the education department is considering installing 40,000 vape detection devices in public schools by July 2024 to reduce the use of vapes.
The state opposition has been contacted for comment.