Police are investigating the cause of a fatal crash at Sandy Hollow on Monday morning.
About 7:50am, emergency services were called to the Golden Highway, after a car and a truck collided.
NSW Ambulance paramedics were the first on scene and began CPR on the driver of the car, however she tragically died at the scene.
Police say the woman is yet to be identified, but is believed to be aged in her 20s.
The driver of the truck suffered only minor injuries and was taken to Muswellbrook Hospital for mandatory testing.
Hunter Valley Police officers have established a crime scene, which will be examined by specialist forensic police.
The Golden Highway remains closed as investigations take place and motorists are advised to avoid the area.
Anyone with information or dashcam footage of the incident are urged to get in touch with Crime Stoppers on 1800 333 000.