The South Korean company, worldwide partner to the Olympic Games, confirmed that the exclusive Team GB smartphones will be available only through the Carphone Warehouse.
Launching in store and online from August 1, the London 2012 Samsung Galaxy S3 comes with a Team GB cover as well as an original cover, enabling customers to easily convert their phone back to the original design after the Games.
Special Team GB designs are available for both blue and white versions of the premium smartphone.
The handset will be available for free on mobile tariffs from £28 per month, including networks options from Vodafone, Orange, O2, T-Mobile, Talk Mobile and Three.
Launched in May, the Galaxy S3 runs Android 4.0 Ice Cream Sandwich and is powered by Samsung's new quad-core processor.
The handset, which has a large 4.8-inch screen, is thought to have sold more than 10m units to date, and is expected to surpass 19m sold by the autumn.
"As a Worldwide Olympic Partner, we at Samsung want everyone to get behind Team GB and offer them support during the Olympic Games," said Simon Stanford, the vice president of Samsung's UK Telecommunications & Networks Division.
"We are delighted to be able to offer Carphone Warehouse customers the chance to own this exclusive London 2012 Samsung Galaxy S3 handset, combining the chance to support Team GB with owning a piece of cutting-edge Samsung technology."
Meanwhile, mobile operators have today said that their networks are braced for the massive increase in demand expected from the thousands of visitors attending London's Olympic Park.