Buffin was European managing director of Groupe Aeroplan, which manages the Nectar scheme, having been promoted from chief financial officer in 2008.
"Tony has extensive retail, finance and business development experience in the UK and Europe," said Coles chief executive Ian McLeod. "I am confident he will make an outstanding contribution to the turnaround of Coles."
Buffin will transfer from London to Melbourne with his family in July. He is the latest in a string of appointments from the UK, following the 2007 acquisition of Coles by Wesfarmers.
Operations director Stuart Machin, himself British, was in the UK last month on a recruitment drive for further UK talent.
Other senior Coles staff who learnt the trade in the UK include merchandise director John Durkan, formerly of Safeway and the Carphone Warehouse, and marketing director Joe Blundell, who worked for Kellogg's, Asda and Shell.
Earlier this month, Gary Hardy, Asda operations manager for south London, was appointed general manager for western Australia, while former Asda chief executive Archie Norman is acting as advisor to the company.
"Coles has sought the best retailing talent to work in Australia - and the best retail talent resides in the UK," said Machin. "We are looking for people with retail experience, not just grocery, as retail skills apply in many sectors."