The State Government will invest $107.7 million into the remediation of the state's abandoned mine sites.
The funding, which will be part of next week's state budget, is part of the Legacy Mines program.
Deputy Premier John Barilaro, who announced the initiative at Mount Thorley/Warkworth Mine on Tuesday, said remedying legacy mine sites would help accelerate economic growth, support jobs and ensure mining communities remain great places to live and work.
"Regional communities were built on the back of mining projects, but these legacy mines were operating at a different time, well before the procedures and requirements we have today for managing chemical use and rehabilitation were put in place," Mr Barilaro said.
"This significant funding boost will allow major remediation works to be completed across ten years at abandoned mine sites, primarily in locations where production ceased between 50 and 100 years ago - in places like Captains Flat and sites in the Central West and Northern Tablelands.
A recent Australia Institute report estimated up to $25 billion could be needed to fill and rehabilitate the Upper Hunter's 23 final voids when open-cut mining ends.
By contrast, the State Government holds just $3.3 billion in environmental rehabilitation bonds for all mines in the state.
Mr Barilaro said the intensive remediation of the mine sites would increase safety, reduce impacts to the environment, and reinvigorate land for other uses such as for community parklands, tourist attractions or select business operations.
Upper Hunter MP Dave Layzell said the additional funding would make a real difference to communities in proximity to higher risk legacy mines.
"As someone who comes from an electorate built on mining at a time when we're fortunate to have safeguards in place to protect people and the environment, I know this will help people feel more confident about living and working around legacy mines," he said.