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The collision happened just after 7am on Third Avenue in Llandilo.
The bus driver was pronounced dead at the scene. There were no passengers on board.
The driver of the car, a police sergeant attached to a specialist command, was treated for head injuries.
He was taken to Westmead Hospital in a stable condition.
NSW Ambulance Inspector Keith Craig said the police officer had been able to get out of the car and call for help, despite his injuries.
“He should be praised for that effort,” he said.
The crash also brought down powerlines.
Police confirmed a critical incident investigation was underway and would be independently reviewed before information was provided to the coroner.