Six people were issued tickets at the Mitchell Avenue rail crossing at Kurri Kurri during a two week enforcement campaign.
Hunter level crossings received additional police patrols between May 27 and June 7 as part of an ongoing safety campaign across the state.
The six penalty notices were issued to drivers who disobeyed stop signs at the crossing, which was the site of two crashes involving trains and vehicles in a seven-month period from August 2017 to February 2018.
The first incident occurred in August 2017, when police said the driver of a car "slowed but did not stop" and was struck by the train despite the train driver sounding horn.
In February 2018, a semi-trailer is alleged to havefollowed a car through the level crossing. The trailer was clipped by the train dislodging part of its load.
In light of the two crashes at the Mitchell Avenue crossing, Traffic and Highway Patrol Command contacted road and rail agencies and organised a meeting on-site in May 2018.
"Whilst road users need to be responsible for their actions, the current 'safe systems' approach to road safety leads to police and other agencies to look beyond the wreckage to see what can be done to prevent crashes from occurring in the first place," Traffic and Highway Patrol Command Senior Sergeant Mick Timms said.
The meeting led to the installation of upgraded signage and line marking at the level crossing.
"Police and Transport for NSW have been running localised level crossing campaigns since 2011," Sergeant Timms said. "One of the aspects of these campaigns is to remind motorists of the importance of obeying traffic controls at level crossings.
"The efforts of Cessnock Council and South Maitland Railway in improving the Mitchell Avenue level crossing leaves motorists in no doubt as to what is required of them.
"We appreciate the efforts of both groups."