The 39-year-old had been on Myrtleford-Yackandandah Road when he was struck near the intersection of Carrolls Road on Saturday night.

Emergency service workers were called to the incident about 11.25pm.

The man was treated by paramedics but died while being transported to hospital.

The driver, 21, was not injured.

He stopped at the scene.

A police spokeswoman said the matter was being investigated.

"The exact circumstances surrounding the collision are yet to be determined and the investigation is ongoing," Leading Senior Constable Natalie Dean said.

She said the driver, who lives in Myrtleford, is assisting police as part of the investigation.

There had reportedly been fog in the area at the time.

The collision, which involved a white Subaru sedan, took the Victorian road toll to 147.

The toll had only been 91 to the same time last year.

Police are running road safety operations in NSW and Victoria as part of the long weekend.

Victorian officers are focusing on areas frequented by holidaymakers, including those heading to the ski fields.

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Trail bike riders are also a focus, along with those travelling on rural roads and people towing trailers and caravans.

Two people have been killed in NSW during the operation, which runs until Monday night.

Assistant Commissioner Michael Corboy urged drivers to be vigilant.

"Fatalities affect a whole community," he said.

"That's two men who did not go home to their families (on Friday) night.

"Motorists and motorcyclists need to remain alert, slow down, and always drive to the weather conditions.

"Not just during this operation, but every time they drive or ride.

"It never gets any easier telling someone that their loved one won't be returning home."

NSW officers had caught 1112 drivers speeding and conducted nearly 50,000 breath tests by Saturday afternoon.

There had been 69 major crashes and 25 people caught drink driving.

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