The blaze, which was downgraded from emergency to watch and act level at 7.30pm, burnt through 200 hectares between Pelaw Main and Buchanan during the afternoon.

At the height of the emergency at 5.30pm residents on Richmond Vale Road were evacuated while those living near Averys Lane were advised it was too late to leave and to seek shelter.

Extra firefighting resources were brought in to support dozens of firefighters and rescue personnel who were fighting the fire.

Two fixed wing aircraft and an aircrane were also used to help battle the blaze.

Firefighters were called into action after the crash occurred about 10.15am on Leggetts Drive at Pelaw Main. Police said they received reports a vehicle had left the road and hit a pole. The vehicle's driver was found dead at the scene and was yet to be formally identified on Tuesday.

Police and firefighters confirmed the crash caused the vehicle to catch alight, sparking several spot fires.

With tinderbox conditions in the Hunter that had sparked three days of continuous total fire bans in the region up until Tuesday, the blazes quickly took hold and began pouring plumes of smoke over the small township.

Leggetts Drive closed in both directions between Neath Street and Lake Road as firefighters battled the flames, with traffic diverted to the Hunter Expressway and M1 Motorway.

In the early afternoon firefighters upgraded the risk of the bushfire.

By 2.30pm, the fire had devoured roughly 34 hectares and seared its way closer to the small village of Pelaw Main under conditions deemed a Very High fire danger.

NSW RFS spokesperson Ben Shepherd said at 3pm that the fire had broken containment lines, but was not posing a threat to properties as almost 50 firefighters worked to quench it.

The fire was moving south-east towards Richmond Vale Road, sparking a precautionary evacuation at Pelaw Main Public School. Students were taken by bus to Kurri Kurri Public School.

Other fires in the Hunter, including the Little L Complex blaze in Yengo National Park near Singleton and the Meads Creek West fire in the Upper Hunter shire, remained at advice level on Tuesday afternoon.

The Meads Creek West blaze, burning near Meads Crossing on the Goulburn River, has eaten 6890 hectares and on Sunday briefly flared to emergency warning level before firefighters gained the upper hand.