A man and a woman have led police officers from two states on a pursuit that at times held all the elements of a good Hollywood script as shots were fired, cars collided and the pair attempted to refuel the vehicle while fleeing from police.

The two were arrested after leading police on a chase from Mungindi to 55km west of Tenterfield. A farmer with a helicopter also assisted police, flying his helicopter above the car chase and providing coordinates until PolAir arrived.

On Friday, police announced charges had been laid.

The 28-year-old man man was charged with police pursuit - not stop - drive dangerously, drive recklessly/furiously or speed/manner dangerous, drive conveyance taken without consent of owner, use offensive weapon to prevent lawful detention, possess unauthorised prohibited firearm, receive property stolen outside NSW, and use offensive weapon in company to prevent detention.

The 27-year-old woman was charged with drive whilst disqualified, drive in a manner dangerous, and drive conveyance without consent of owner.

Both were refused bail to appear at Armidale Local Court on Friday 20 September 2019.

District Commander for New England Scott Tanner, speaking at a press conference at Armidale on Thursday, said the attempted refuelling clearly demonstrated the tenacity of the alleged offenders to avoid arrest.

"The male offender was leaning outside the passenger window trying to fill up the vehicle from a jerry can while the vehicle was still in motion," he said.

"His actions clearly indicated their intent to get away from police. He was not successful."

The chase began in the back streets of Mungindi at about 6.30 on Thursday morning when police noticed a suspicious vehicle with two people inside. When approached, the two rammed the police car.

"That vehicle was then tracked towards Boggabilla. When the vehicle was about 10 kilometres south of Boggabilla police will allege that the male occupant fired a shot towards police."

Supt Tanner said the operation involved more than 30 police who were drawn from all areas

"We had police from the Rural Crime Prevention Team, Highway Patrol," he said. "We then sought and received assistance from our colleagues in Queensland who sent over general duties police and also sent a contingent of their Special Emergency Response Team by helicopter.

"We also had our Tactical Operations Unit from Sydney flown to the scene."

He said investigations are ongoing and no charges had been laid.

EARLIER:

A POLICE chase that lasted hundreds of kilometres has ended in a dramatic arrest on the Bruxner Highway.

A man and woman are now in custody in Tenterfield after a couple fired shots at officers and rammed a police car at 7am in Mungindi, Queensland.

The car was rammed when police responded to reports of a suspicious grey Mazda parked behind the shops in St George Street.

A check of the vehicles number plate revealed it was reported stolen more than a thousand kilometres away in Cairns.

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When police approached the car, the driver accelerated and collided with the front of it before speeding off.

A police pursuit began and the couple fired shots at officers, but no one was injured.

Specialist resources from both NSW and QLD were deployed to the operation.

The car eventually stopped in the middle of the Bruxner Highway and traffic diversions were put in place.

At about 11:30am, police arrested a 28-year-old man and 27-year-old woman.

The pair were taken to Tenterfield Police Station where they are being questioned.

Investigations are continuing.

Police have thanked the public for their assistance, including a local farmer who flew his helicopter above the car chase and provided coordinates until PolAir arrived.

New England Police District officers will hold a press conference this afternoon to address the media on the details of the incident.