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A man has died in his burning car after colliding with a truck in NSW's Hunter region.

The crash between the man's Toyota Corolla and the truck occurred about 5.10am on Thursday between Muswellbrook and Merriwa on the Golden Highway, about 15km north of Sandy Hollow.

Police say the Toyota caught fire, trapping the driver inside.

"Despite the attempts of other motorists and emergency services to free the man, he died at the scene," police said in a statement.

The truck driver was not injured but was taken to Merriwa Hospital where he will undergo mandatory blood and urine tests.

The Golden Highway was closed while officers examined the scene and police will prepare a report for the coroner.

In a second road fatality in the Hunter region, a truck driver died after losing control of his semi-trailer at Howes Valley near Singleton at about 7:40pm on Wednesday, police said.

''The truck, laden with turf, failed to negotiate a bend and rolled onto its side, crushing the cabin.

''The driver, believed to be aged in his 30s, was trapped inside the vehicle and died at the scene."