Yancoal announced on Thursday that Li had been appointed as a director and as chairman following the resignation of former chairman Li Wiemin, who said in July he was stepping down "due to work allocation".
Li Xiyong has more than 30 years of experience in the industry and in 2011 was appointed as the vice chairman of Shandong Energy Group.
Earlier this year he also became the general manager of the Yankuang Group.
Li was appointed to the position of chairman at Yancoal’s parent company and key shareholder Yanzhou last week.
There has been a considerable staff shuffle at Australia-listed Yancoal of late, with Reinhold Schmidt, a former senior executive at Glencore Xstrata, last month named as chief executive to succeed Murray Bailey, who stepped down mid-March.