Emergency services were called to a home on Traders Way in Heddon Greta, 20km east of Cessnock, after reports a man had been shot around 11pm.
Paramedics tried to revive the man but he died at the scene.
He is yet to be formally identified but is believed to be aged 25.
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”Officers from Hunter Valley Police District established a crime scene, which will be examined by specialist forensic police,” NSW Police said.
Investigations are continuing.
Anyone with information, CCTV or dashcam footage of the area at the time of the shooting is urged to contact police.
