Police have confirmed officers had tried to stop the vehicle in question before it collided with an oncoming four-wheel-drive on Werris Creek Road on Tuesday afternoon.

A spokesperson for NSW Police said the vehicle of interest was seen driving in a manner dangerous by officers from Peel Highway Patrol at about 2pm.

Officers tried to stop the vehicle but a pursuit ensued along Werris Creek Road from Quirindi towards Werris Creek.

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"When the northbound vehicle attempted to turn right into Lowes Creek Road, it collided with a black Ford Territory travelling south towards Quirindi," the spokesperson told the Leader.

"Highway patrol, Oxley police, paramedics, Fire and Rescue NSW, the VRA and other emergency service personnel attended the scene and rendered first aid to the occupants of both vehicles."

Police said the female driver of the black Ford Territory - who was headed home to Quirindi - suffered serious injuries including a fractured ankle.

The driver of the other vehicle suffered serious knee and arm injuries, while a woman, who was a passenger in the car, was also injured.

"All three were taken to Tamworth hospital for treatment, where they remain," the police spokesperson said.

Crash investigators were deployed to the scene and spent several hours examining the area.

The collision and the moments leading up to it were captured by an on-board dash camera in the police vehicle.

Investigations were continuing on Wednesday but no charges have been laid.

The road reopened overnight after the wrecks - which will be examined as part of the police investigation - were cleared.

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