A woman, allegedly walking on the Hume Highway, has died after being hit by a car near Goulburn early on Thursday morning.

NSW Police say that at about 4am emergency services were called to the Hume Highway, near Sydney Road, Boxers Creek, following reports a pedestrian had been hit by a car.

Police were told a woman had been on the road when she was hit by a four-wheel-drive travelling in a north bound lane.

Ambulance paramedics treated the 32-year-old woman at the scene, before she was taken to Gouburn Base Hospital where she later died.

The 63-year-old male driver of the four-wheel-drive, was taken to hospital for mandatory testing.

A report will be prepared for the coroner.