The Good Friday toll grew significantly about 6.45am after four people were killed and one person was injured in a two-car crash in the Southern Tablelands of NSW, near the ACT border.
The victims of the crash on the Barton Highway at Jeir included a woman and three men, who died at the scene, while another man sustained critical injuries.
A motorcyclist also died on the NSW North Coast on Friday, NSW Police acting assistant commissioner Tracy Chapman said.
The motorcyclist was involved in a collision with a Nissan Patrol on Waterfall Way at Hernani about 9.30am, with the dead rider believed to be aged in his 20s.
The male driver of the Nissan, 23, was uninjured.
NSW Police is running a major traffic operation cracking down on road trauma through the long weekend.
On day one of the operation, Thursday, officers caught almost 40 people drink driving, almost 70 tested positive for drugs, and more than 600 people received speeding tickets.
"Police will investigate those (fatal) matters and will be out and about for the remainder of the operation," Ms Chapman said.
"The message is pretty simple: drive to the speed limit, drive to the conditions, don't drive while under the influence of drugs and alcohol (and) certainly have a plan B if you are intending to drink.
"Focus on the road and not your phones. That is the message we need motorists to heed to make sure that we have an incident-free weekend."
In Victoria, a car came off Holdsworth Road at White Hills in Bendigo about 3.15am on Friday, subsequently crashing into a tree and catching fire.
The driver, who is yet to be identified, died at the scene, with Victoria Police yet to determine the exact circumstances of the crash.
A woman died after a two-car collision on the Arthur Highway at Copping in Tasmania's southeast about 9.20am on Friday.
The crash occurred between a silver Toyota Camry sedan and a white MG sedan, with the woman a passenger in the MG.
The MG's male driver was hospitalised with minor injuries, as was the female driver and passenger of the Camry.
A baby in the Camry was uninjured in the crash.
"Our thoughts are with the woman's family and loved ones at this tragic time," Tasmania Police said.
Queensland Police on April 1 launched Operation Victor Easter.
Officers in the state have charged more than 340 people with drink driving since the start of the school holidays.
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