A woman has died in a head-on crash with a van on a NSW South Coast highway.

The 81-year-old driver became trapped in her Volkswagen Jetta when it collided head on with a Toyota HiAce van on the Princes Highway at Narooma about 12.15pm Thursday.

Emergency services were able to free the woman after a short time. She was treated by paramedics but died at the scene.

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The Toyota driver, a 42-year-old man, was flown to Canberra Hospital with leg fractures.

A crime scene has been established and police are investigating how the tragedy unfolded.

A report will be prepared for the coroner.

Anyone with information is asked to contact Crime Stoppers on 1800 333 000 or report online.