Riverina Police District Acting Inspector Nige Turney said the woman was driving a silver Mitsubishi Lancer along Canola Way about 1.30pm on Thursday before leaving the road for "an unknown reason".

He said the car hit a tree about five kilometres east of Matong.

"The driver was able to be removed and able to be treated at the scene, but due to the nature of their injuries, they died at the scene," he said.

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Acting Inspector Turney said the tragedy came as an unfortunate reminder of the need to be careful on country roads, saying they "can be difficult to navigate".

Narrandera Volunteer Rescue Association squad captain Wayne Heidtmann said he attended the scene of incident along with other emergency services.

Mr Heidtmann said he and other rescue volunteers removed the patient from the vehicle for paramedics, who arrived in two ambulances.

Officers from Riverina Police District attended and established a crime scene, which was examined by specialist forensic police.

An investigation into the circumstances surrounding the crash is underway and a report will be prepared for the information of the Coroner.