NSW police stations in Sutherland, Penrith, Narellan, Grafton, Griffith and Dubbo will accept surrendered guns from November 2, with a further 34 ready to receive excess firearms from December 1.
The number of firearms allowed per person will be restricted to four while primary producers and sporting shooters will be allowed a maximum of 10.
The buyback will compensate people for firearms they can no longer legally own.
NSW was the first - and only - state to sign up to the federal government's beleaguered buyback, the largest scheme since a Howard-era program followed the 1996 Port Arthur massacre.
On Monday, Queensland Premier David Crisafulli continued insisting he would "absolutely not" take part despite a Saturday drive-by shooting in Brisbane that left four injured.
"Good people should be able to have weapons. Bad people should have none. Terrorists and crooks should never have a gun - not one or three or five but zero," he told reporters.
"We have laws to make sure people who are crooks and terrorists are held accountable and not innocent people."
NSW Police Minister Yasmin Catley defended the national program's ultimate aim of reducing firearms in circulation.
"Fewer guns in the community means a safer community. It means fewer guns at risk to fall into the wrong hands," she said.
About one in 33 people hold a gun licence in NSW with more than one million individual firearms legally registered - the most in Australia.
About 18 per cent of licence holders will be eligible to participate in the scheme and up to 274,000 firearms could be surrendered in NSW.
Grants of up to $25,000 will be available for eligible businesses and dealers, with one-off licence fee relief of $500 per gun dealer.
Gun shop owners and shooting groups have slammed the move for putting them out of business.
The NSW Firearms Registry, which received $43 million to tighten intelligence gaps, will contact eligible licence holders starting on Monday.
Tough national gun control laws were ushered in after the 2025 Bondi attack in which 15 people were killed.Â
Sajid Akram, one of the two shooters who was killed by police, legally owned six guns at the time.
The buyback scheme has faced opposition from some jurisdictions although the ACT has also agreed to take part.
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