Masters joins the retailer from Threshers' owner First Quench Retailing, where he is currently executive director for property and retailing services. He has a wealth of experience in the property sector, developed during his time with a range of UK and international retailers.
Masters will join Asda in the autumn, taking over from Rob Swyer. He will report to Asda chief operating officer Andy Clarke.
"Steve brings with him extensive knowledge of the property sector, which will strengthen the property and construction teams, making sure we are best placed to continue to play a leading role in the property sector opening new space across the UK and improving our existing stores," said Clarke.
Asda hoped to expand its store base across the UK despite the impact of the economic slump on the UK property market, he added.
"We have recently acquired three stores from The Co-operative Group and will open eight new food stores and four Living stores in the remainder of this year, creating hundreds of new jobs," he said.
Masters added: "I am looking forward to joining the UK's best-value food retailer and working with my new colleagues in retail development. We have a great opportunity to bring what Asda has to offer to new communities across the country and provide our customers with the best possible stores to shop in."