Emergency Services were called to Booral Washpool Road at Stroud about 75 kilometres north of Newcastle after reports of a car crash about 7am.
Police were told a motorcyclist and a Holden Captiva collided.
The rider died at the scene.
The man is believed to be in his 50s, but is yet to be formally identified.
The 62-year-old female driver of the car was taken to Dungog Hospital for mandatory testing.
A crime scene has been established while police investigate the circumstances surrounding the crash.
A report will be prepared for the Coroner.
