The driver of a bus which rolled, killing 10 people and injuring dozens more after a wedding at a NSW winery, will face court charged with a slew of dangerous driving offences.

Brett Button, 58, was taken to hospital for mandatory testing and arrested following the accident in the Hunter region on Sunday night.

He was on Monday charged with 10 counts of dangerous driving occasioning death and one count of negligent driving occasioning death.

He was refused bail and will appear at Cessnock Local Court on Tuesday, NSW Police said.

Ten people were killed and 25 taken to hospital with varying injuries after the crash at a roundabout on Wine Country Drive near Greta in the Hunter Valley.

Premier Chris Minns said 14 people remain in hospital as authorities work to ensure they get the care they need.

"... Everybody in the state has been really traumatised by these terrible events," he told Nine's Today show on Tuesday.

A trauma counselling centre will open in Singleton youth centre on Tuesday to help anyone affected by the tragedy.

"It's available for the community to come and get trauma counselling and speak to health professionals if they need to," Mr Minns said.

"It's the government's responsibility and the local council's responsibility to be there for them not just in the immediate glare of the accident but in the weeks and months to come."

Acting Assistant Police Commissioner Tracy Chapman on Monday described the confronting crash scene.

"Emergency responders ... were able to smash the front windscreen of the bus in order to pull some people out," Ms Chapman said.

The bus was returning guests from a wedding reception at Wandin Estate winery in Lovedale to Singleton, about 20 minutes away.

It was a tragic end to the fairytale wedding of Mitchell Gaffney and Madeleine Edsell, who are highly involved with local AFL club the Singleton Roosters.

The Warrandyte Cricket Club in Victoria, where Mr Gaffney is understood to have lived until 2017, said a number of its members were involved in the crash.

Police have begun taking witness statements from survivors.

"They're providing a version of, or witness statement in terms of what they experienced and that will assist us with our inquiries and furthering that investigation," Ms Chapman said.

Police Commissioner Karen Webb said the use of seatbelts would undoubtedly be one of the matters looked at by the coroner.

"Whether they were actually wearing seatbelts or not ... certainly all of that will come under scrutiny," she said.

"Again that will be a matter the coroner will have a look and ultimately the driver will have to think about that for the rest of his life."

© AAP 2023