Talbot stepped down from the board this morning to give himself "greater flexibility to fully deal" with his remaining 19.76% stake in Macarthur.
Last month ArcelorMittal took a 14.9% stake in Macarthur, 4.3% of which came from Talbot's holding in the company.
While several steelmakers have shown interest in Talbot's remaining stake, Macarthur said last week it was still in talks with ArcelorMittal.
Talbot said his resignation was in Macarthur's interest.
“I wish Ken every success in his future endeavours and on behalf of the board and staff at Macarthur Coal, I extend our sincerest thanks to Mr Talbot for developing this company into what it is today," Macarthur chairman Keith De Lacy said.
Talbot stepped down as managing director of Macarthur 18 months ago when facing 35 counts of corruption for making payments totalling $300,000 to former government minister Gordon Nuttall between 2002 and 2005.
He said today the circumstances surrounding his departure as MD led him to review and identify the wider opportunities which exist within the resources sector.
"As someone who is particularly attracted to greenfield opportunities and developing new assets, my energy will be directed towards those activities in the future," Talbot said.
Just last month Talbot took a 5.97% stake in Australian-listed Riversdale Mining which owns coal assets in South Africa and Mozambique.
"Looking ahead I predict a bright future for Macarthur and PCI coal which we have pioneered, and wish to thanks all my joint venture partners, customers and loyal supporters of the company over many years."