Emergency services were called to a property in Pokolbin, about an hour's drive west of Newcastle, over welfare concerns, just after 6pm on Friday.
Officers found a 46-year-old woman with significant injuries who could not be revived, police said in a statement.
"Initially, police did render first aid but shortly after that, it had become apparent that was unsuccessful," Hunter Valley Police Acting Superintendent Steve Benson told reporters on Saturday.
The call to police came from a family member on the property and the woman's 47-year-old husband was arrested without incident, Supt Benson said.
"It was a confronting scene and we've put a lot of support around those officers and emergency services that attended ... and for the family of the deceased," he said.
The man was charged with one count of domestic violence-related murder and was denied bail by police at Newcastle Bail Court on Saturday.
He will next face Newcastle Local Court on Monday.
The crime scene is expected to be finalised on Saturday as police establish a strike force to investigate the death.
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