About 9am on Saturday, emergency services were called to Goldfields Way, between Old Junee Road and Canola Way, after reports that a Mitsubishi Sedan had left the road and hit a tree.

The driver, believed to be a 23-year-old female and sole occupant of the vehicle, died at the scene.

Junee Shire Mayor Neil Smith said the incident was tragic and that any death is hard.

"But doubly difficult when it's a young life," he said.

"She was a young person beginning her life, but it's tragic wherever and whoever it is.

"She would've had so much potential, so to have that taken away early is difficult for anyone."

The Riverina Police District's commander, Superintendent Bob Noble, said it was a terribly sad incident and confirmed that the woman was a resident of Old Junee.

"The family's devastated, the community's devastated," he said.

"It'd have a ripple effect across the entire district, I'm sure.

"When a person loses their life at such a tender age, with so much in front of them, there's no upside here."

He said the incident happened near her home and urged motorists to adhere to safe driving and road rules, particularly now that it is school holidays.

On Saturday, NSW Ambulance Inspector Eamon Purcell said initial reports indicated that the patient was critically ill, which attracted a large response including a helicopter from Canberra and three road crews.

"This is such a tragedy and a waste of young life, so it serves as a timely reminder for all motorists to take care on the roads particularly during the school holiday period that is upon us," Inspector Purcell said.

He also thanked a registered nurse who stopped by the accident scene and called triple zero.

"The nurse provided invaluable assistance prior to the arrival of paramedics and we are grateful for her support," Inspector Purcell said.

A crime scene was established and a police spokesperson on Sunday said no further information was available as inquiries continue. Traffic diversions were in place until about 6pm on Saturday.