The Bells Line of Road was closed on Monday and Great Western Highway cut off for drivers east bound following the two accidents on the two main roads over the Blue Mountains.

Significant diversions were in place for much of the day, with huge delays for motorists on the first day Greater Sydney has been allowed to travel to regional NSW following the lifting of COVID-19 restrictions in NSW.

At around 10.30am on November 1, emergency services were called to the Bells Line of Road at Mount Tomah after a truck and a car collided, trapping both drivers and their passengers.

NSW Police Rescue, with help from Fire and Rescue NSW, NSW SES, and NSW Ambulance paramedics worked to free the occupants.

The driver of the car - a 76-year-old man - died at the scene.

The car passenger - a 75-year-old woman - along with the driver of the truck - a 60-year-old man - were airlifted to hospital in a serious condition.

The passenger of the truck - a 48-year-old woman - suffered minor injuries and was taken to hospital by road ambulance.

Officers from Blue Mountains Police Area Command and the Crash Investigation Unit established a crime scene and have commenced an investigation.

Across at Blaxland on the Great Western Highway, a disqualified driver has been charged following a fatal pedestrian collision at around 2pm on November 1.

Emergency services were called to the Great Western Highway, near the intersection of Layton Avenue, at Blaxland, following reports a pedestrian had been struck by a truck.

The pedestrian - a 21-year-old woman - who had reportedly been walking on the footpath at the time, was treated by NSW Ambulance paramedics; however, died at the scene.

The truck driver - a 54-year-old man - was not injured and taken to hospital for mandatory testing, before being taken to Katoomba Police Station.

He was charged with dangerous driving occasioning death - drive manner dangerous, drive motor vehicle during disqualification period and negligent driving (occasioning death).

The Penrith man was refused bail and is due to appear at Penrith Local Court on November 2.

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

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