Apple's iPhone 3G and 3GS will be available in 402 Orange stores, Orange online, Orange HMV concessions, The Carphone Warehouse and Phones4U outlets.
Last month, Orange signed a deal with Apple to bring the iPhone to customers. Rival network Vodafone has signed a similar deal with Apple.
O2, however, will continue to offer the phone to its customers after having an exclusive UK distribution deal since 2007.
Tom Alexander, chief executive of Orange UK, claimed around a quarter of a million Orange customers have already registered an interest in taking the iPhone.
The distribution of the iPhone by Orange UK will mean it now offers the Apple handset in 28 countries worldwide.
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