About 2.30am Friday, emergency services were called to Cessnock Road, Maitland, following reports a Kia Rio and a Ford Falcon sedan had collided head-on.

The female driver and sole occupant of the Kia Rio, believed to be 45 years of age, died at the scene and is yet to be formally identified.

The male driver and sole occupant of the Ford Falcon sedan, believed to be in his 70s, sustained a back injury.

He was taken to hospital for treatment and will also undergo mandatory blood and urine testing.

Officers from Port Stephens-Hunter Police District with assistance by officers from the Newcastle Crash Investigation Unit will investigate the circumstances surrounding the crash.

Cessnock Road was closed between the New England Highway and Gillieston Road while the scene is being examined.

The road has now reopened in both directions.

At this stage, there is no indication of the cause of the crash. Police investigations are continuing.

A report will be prepared for the information of the Coroner.