At about 9.35 pm yesterday evening, police received a report of a head-on collision between two cars, both Vauxhall Astra, on the A710 between Dalbeattie and Kippford.
Emergency services attended and the woman was pronounced dead at the scene.
The other occupants of the vehicles – two men aged 83 and 23 and a 20-year-old woman – were taken to Dumfries and Galloway Royal Infirmary and remain in hospital.
The road at the scene was closed for several hours while investigations were carried out.
Sergeant Paul Dodds said: “An investigation is underway to establish the circumstances of the crash.
“I am appealing to anyone who was on the A710 around the time of the incident to contact us.
“In particular, I’m asking motorists with dash cams to check their footage and hand in any images which could assist us in our enquiries.”
Anyone with information is asked to call road policing officers at Dumfries via 101, quoting incident number 4370 of May 23 2019.