Eight firearms, MDMA and other drugs were seized in the statewide operation launched after the Task Force Erebus arrests of 18 people in Sydney on Tuesday.
NSW Police Commissioner Karen Webb said a police operation under way for more than 10 months had culminated in the execution of 30 search warrants and 18 arrests on Tuesday.
Strike Force Hawke made more arrests since then, taking the taking the number to 63, with 50 search warrants executed.
"On top of that, we've seized 36 mobile phones that we allege have been used in the syndicate and that will go a long way to breaking that syndicate," Ms Webb said.
"We've also arrested a gentleman last night, yesterday, for facilitating that access to those mobile phones and SIM cards."
"It's a very organised network, right from the importation through to the distribution and street level supply.
"So we've really smashed this network.
"We will allege that the supply of drugs through this phone network has actually been part of the turf war that has led to people being murdered.
"So from low-level crime right through to the worst crime and certainly well-organised, orchestrated, and it's very complex web of people and syndicate."
Ms Webb said police were confident Sydney remained safe and the people involved were a relatively small group.
She said many of those involved had been arrested.
Detective Superintendent Jason Weinstein said the Operation Hawke sweep involved specialist units and commands across NSW.
"NSW attracts around 40 per cent of Australia's national organised crime population - many of whom attempt to evade the attention of police by operating outside of the Sydney metropolitan area," he said on Friday.
Police estimate the sale of prohibited drugs in NSW is worth at least $3.7 billion a year at street level.
Police say 23 kilograms of ecstasy, 2.5kg of cocaine and a substance suspected of being methamphetamine, collectively worth an estimated $4 million, were seized at two properties at Fairfield in Sydney's west on Tuesday afternoon.
In the Hunter Valley, a search at the home of a Life and Death bikie gang member recovered two rifles a pistol, 350 rounds of ammunition, gel blasters, an electronic stun device, drugs and cash on Wednesday.
The 49-year-old has been charged with 33 offences.
Two revolvers were also found during a stolen car search at Summer Hill in Sydney's inner west, while a shotgun, other prohibited weapons, drugs, $30,000 cash and stolen goods were seized in Riverina house raids in southern NSW.
