Regional drivers have been reminded crashes can happen anywhere and at any time, irrespective of how well they know a particular road.
The warning comes after three of the four deaths on the state's roads during the Queen's Birthday long weekend were in southern NSW.
Among the fatalities was a 25-year-old Bomaderry man, who was killed in a crash on Gerroa Road near Berry on Saturday afternoon. Police believe the driver lost control while trying to overtake southbound traffic. His ute left the road and hit a tree.
He was unable to be revived and died at the scene.
A 24-year-old passenger was flown to St George Hospital, where he remained in a stable condition on Tuesday.
Elsewhere, a 91-year-old man was killed in a multi-vehicle crash north of Crookwell on Friday, while another driver lost his life when his Nissan Patrol hit a tree near Tocumwal, in the southern Riverina, on Sunday.
Officers across the NSW Police Force's southern region - which covers eight police districts, from Wollongong to the Victorian border and inland as far as the western Riverina - issued 950 speeding tickets during the four-day police road safety blitz, Operation Stay Alert.
Almost 44,000 breath tests were conducted, resulting in 45 PCA charges.
There were 46 seatbelt offences and 29 major crashes, with 14 people injured.
Among the people injured was a 35-year-old male motorcyclist, who police say failed to stop at a random breath testing site on Five Islands Road at Cringila about 9pm on Monday.
Officers patrolled the area and were called to a crash in a nearby suburb minutes later. When officers arrived they found a motorcycle and B-Double had collided on Flinders Street, Port Kembla.
The rider sustained serious arm, face and other injures. He was taken to hospital. Police said they would speak with him when his condition allows.
With three-quarters of the fatal crashes over the June long weekend happening on rural roads, police have warned motorists of the potential dangers when driving well-travelled thoroughfares.
Assistant Commissioner Michael Corboy, from NSW Police Traffic and Highway Patrol, said drivers must "be prepared for the unexpected and drive to conditions".
Asst Comm Corboy said several fatal crashes at the weekend involved vehicles leaving the road and hitting other objects.
"While the causes of all the crashes on the weekend are still under investigation, I would encourage all drivers or riders to be aware of their surroundings and take breaks if they are tired," the senior officer said.
"It doesn't matter where you are travelling to - crashes do not discriminate.
"They can happen anywhere and at any time."