Cario stepped down from his position at Austral mid-April after Centennial Coal gained control of the company.
Cario holds more than 26 years in the Australian coal mining industry, including eight years as managing director of Austral.
Prior to Austral, Cario held a number of senior positions with Conzinc Rio Tinto Australia Group. He was also a director of Port Kembla Coal Terminal, the New South Wales Joint Coal Board and in 2004 was the interim NSW Minerals Council chairman.
Cario will take over from Matthew Abrahams.