The bus was returning guests from a wedding reception at Wandin Estate Winery in Lovedale to Singleton when it overturned at around 11.30pm on Sunday.
Guests had travelled from Melbourne, Queensland, Byron Bay and Sydney to attend the event which turned from a day of celebration into tragedy.
Rebecca Mullen, a junior doctor and Singleton local working at Calvary Mater Newcastle hospital, was one of the younger victims to die in the crash.
NSW Health Minister Ryan Park said Ms Mullen had ahead of her a "long and illustrious career in medicine" but she was taken too early.
"This has made a very dark day even darker for NSW Health," Mr Park told reporters on Tuesday.
Singleton husband and wife Andrew and Lynan Scott also died in the crash, reportedly leaving behind two young sons.
Nadene McBride and her 22-year-old daughter Kyah were also killed, while husband and father Graham "Banger" McBride remains in hospital, coming to terms with his loss.
"There are no words to describe the grief our family is feeling at this time," the McBride family said in a statement.
The family were heavily involved with the Singleton Roosters AFL team, with Nadene the club president and Kyah playing for the Singleton Roosterettes.
Kyah's boyfriend, Kane Symons, also died in the crash.
His former Tasmanian Carlton Park Surf Life Saving Club paid tribute to the keen surfer, describing him as an extraordinary athlete, a remarkable leader and a genuine friend.
"Kane's infectious enthusiasm, positive spirit, and constant encouragement have left an indelible mark on our club, and his loss will be deeply felt by all who had the privilege of knowing him," club president Christine Gaby said in a statement.
A GoFundMe page set up on Tuesday by the Singleton Roosters club says its committee and club members aim to raise funds to help the families involved.
"For Nads & Kyah. The world shines less bright with your sudden loss," one contributor wrote.
Another victim, Tori Cowburn, was a Singleton local and mine worker who captained the Roosters in the close-knit community.
Hunter Valley mining engineer and bowel cancer survivor Zach Bray was also among those killed.
Originally from Sydney's northern beaches, his father Adam spoke of his pride in his son.
"Zach Bray … (you) have become a giant of a man in every possible way, proud doesn't even come close," he wrote on social media.
Another victim of the crash was Melbourne woman Darcy Bulman who worked as an investigator for the Australian Securities and Investments Commission since late 2020, a spokesman confirmed.
Singleton Mayor Sue Moore said her close-knit community was struggling to come to terms with the extent of the loss after enduring previous tragedies during bushfires and floods.
"This is a whole different level, of course, with seven lives lost," she told ABC TV on Tuesday.
Singleton was a small community which meant locals were likely to have a connection to victims, Ms Moore said.
Cessnock Mayor Jay Suvaal said the city was in shock but would support its neighbours in Singleton.
The owners of local hotels have begun offering accommodation to the victims' families, with many needing extended stays in the area.
"We want to make sure people have got the support services they need," Mr Suvaal said.
The bus driver, Brett Button, 58, faced Cessnock Local Court on Tuesday charged with 10 counts of deadly dangerous driving.
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