A man suspected of stabbing a woman and dousing her with petrol has been shot dead during a confrontation with police on the mid-north coast of New South Wales on Thursday.

Police were called to a home in Port Macquarie about 7pm following reports a woman had been stabbed repeatedly during a domestic attack.

They said the 28-year-old was also covered with petrol during the assault, before she was rushed to hospital in a serious condition.

About 9:45pm police pursued a 36-year-old man along the Pacific Highway at Bonville, before attempting to stop and arrest him.

They said the man died during a confrontation in which an officer fired their gun.

Police have launched a critical incident investigation.

Temporary road blocks are in place on parts of the Pacific Highway.

More to come.