Illawarra Coal welcomed nine university graduates to the company on Tuesday.
The newest employees were selected through BHP Billiton's three-year graduate program, which attracted more than 9000 applicants.
Illawarra Coal's head of external affairs John Brannon said the company got the "best of the best" applicants.
"We are looking forward to building our professional skills base for the future," he said.
The graduates will gain experience in mining, mechanical and electrical engineering, geology, surveying or communications.
UOW electrical engineering graduate Steven Sultana did vacational work for Illawarra Coal before applying for a graduate position.
"I've always had a passion for electrical engineering," he said.
"I think this program will definitely test everything I learnt at university."
Mr Sultana applied for the program because of its highly structured nature.
Technical specialists mentor the graduates, who are given a position with the company at the end of the program.
UOW science-commerce graduate Nicola Curtis will be trained in geology.
"Mining is a great way for a geologist to gain experience and training," she said.
Graduates will rotate yearly between Appin, West Cliff and Dendrobium mines.