The two vehicles collided along Putty Road in Howes Valley, about 50km south-west of Singleton, about 10.35am today.
The rider, a 21-year-old man, died before emergency services could get to the scene.
The driver of the Hilux, a 48-year-old man, walked away without injuries and was taken to Singleton Hospital for mandatory testing.
A report will be prepared for the coroner.
Putty Road between Putty and Milbrodale has been closed and is expected to remain a coronial scene for a “considerable amount of time”, police said.
Motorists are advised to avoid the area.
Anyone with information or dashcam footage is urged to contact Crime Stoppers.
