John Browett has been named the senior vice president of retail at Apple, reporting directly to the firm's new chief executive Tim Cook.
Browett, who joined Dixons in 2007, will start at Apple in April, overseeing the firm's retail strategy and continued expansion of its stores around the world.
Apple recorded record iPhone sales in the final quarter of 2011, helping it generate record quarterly net profit of $13.06 billion (£8.36bn), up a staggering 118% year-on-year.
According to research group Canalys, Apple also overtook Hewlett-Packard in the fourth quarter to become the world's biggest seller of PCs, boosted by strong demand for its iPad tablet computers.
"Our retail stores are all about customer service, and John shares that commitment like no-one else we've met," Tim Cook said.
"We are thrilled to have him join our team and bring his incredible retail experience to Apple."
Browett will be replaced at Dixons Retail, which is worth around £550m and owns Currys and PC World, by group operations director Sebastian James.
James will be assisted in running the group by Dixons' new head of UK and Ireland Katie Bickerstaffe.
Dixons chairman John Allan thanked Browett for his "very considerable contribution" to the company over the last four years.
"The group is now in a significantly stronger position and can look to the future with confidence. I wish him well for the exciting opportunity ahead," said Allan.
"We are fortunate to have, in Sebastian and Katie, two extremely strong retailers with tremendous experience who will bring continuity to the progress we are making as a group."
Browett added: "Dixons Retail is a great business, and with the support of a very strong management team we have made excellent progress in transforming the group into the leading customer-focused specialist electrical retailer in its markets.
"The opportunity ahead of me is an exciting one and I leave knowing that the group has a bright future under strong leadership."
Shares in Dixons have increased by more than 50% over the last month, but the stock price fell sharply on the news of Browett's departure.
> Apple.com second most visited retail website in UK