The 42-year-old was driving his family home from a holiday when he's alleged to have crossed to the wrong side of the road, causing the crash which ultimately killed an elderly woman and a four-year-old girl.

Crash investigators from Tamworth have been piecing together the moments before the crash and announced on Tuesday morning they had charged the Tamworth man.

The 42-year-old is alleged to have veered onto the wrong side of the road on the Thunderbolts Way at Nowendoc on Saturday before crashing his four-wheel-drive into the oncoming sedan.

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The 72-year-old woman driving the sedan died at the scene. She was the only occupant in the car.

A four-year-old girl who was a backseat passenger in the four-wheel-drive suffered critical injuries and couldn't be saved. She died en route to John Hunter Hospital in Newcastle.

A 34-year-old woman and three other children inside the four-wheel-drive were also rushed to hospital in Newcastle by the Westpac Rescue Helicopter.

Police confirmed the woman and the two boys, aged nine and 12, as well as a two-year-old girl, suffered various injuries and were treated in hospital for fractures, abrasions and stomach injuries.

The driver - who was also towing a campervan - was treated on scene for minor injuries before he was taken to hospital for mandatory testing, police confirmed.

The crash occurred about 12.20pm on Saturday and saw the road closed for several hours as a crime scene was declared and police combed the scene.

After three days of investigations, the man presented to police in Newcastle where he was charged with several offences.

He's accused of two counts of dangerous driving occasioning death; dangerous driving occasioning grievous bodily harm (GBH); negligent driving occasioning both death and GBH; four counts of causing bodily harm by misconduct while in charge of a vehicle; and not keeping left of the dividing line.

The man was granted bail by police after he was charged. He's been ordered to appear in Tamworth Local Court in mid-October.

The road was reopened on the weekend after it was examined by crash investigators and forensic officers.

The wrecks of both vehicles will also be examined as part of the police investigation.

Investigations into the crash continue.