From October, Sky subscribers will be able to watch all 22 official Bond titles from EON Productions on Sky Movies Showcase, from Dr No in 1962 to the last Bond film, Quantum of Solace, starring Daniel Craig as the iconic British spy.
The two non-EON titles, 1967's spoof Bond Casino Royale and Never Say Never Again, will also be available to Sky Movies customers.
All the movies will also be shown 'side-by-side' on Sky Movies Showcase in standard and high definition. They will also be offered in the Sky Movies section of video on-demand service Sky Anytime, and on the Sky Go multiplatform service available to all Sky customers.
The rights deal marks the first time that the complete catalogue of Bond movies has been made available uninterrupted and in high definition (HD) in the UK.
Sky stressed that the movies will be available "without commercial reference", following the previous deal in which ITV aired all the Bond films in SD and HD in 2010 and 2011.
The licensing deal also coincides with the 50th anniversary of the first film, Dr No, being released on October 5, 1962.
Ian Lewis, the director of Sky Movies, said that everything about the Bond films is "iconic", from the cars to the gadgets to the catchphrases.
"They've become hugely significant culturally; demonstrating the best of British film. It's an honour for us to have all of them for our customers, and we will ensure that we do them justice across Sky Movies, giving our customers the best possible experience in watching them," he said.
"It's an exciting time for Sky Movies and this is just one of many exciting plans we have coming up in the months ahead."
MGM president of international television distribution & acquisition Chris Ottinge added: "It is the first time that the entire Bond collection will be shown side-by-side on one channel and we are really pleased to be able to showcase all of the British classics on Sky Movies."
The upcoming 23rd Bond film, Skyfall, will be released theatrically on October 26, 2012 in the UK, and then arrive on Sky Movies Box Office and in the new Sky Store on Sky Anytime+ in the spring of 2013.
Sky's review programme 35MM will broadcast behind-the-scenes footage and exclusive interviews from Skyfall to coincide with the arrival of the James Bond collection on Sky Movies in October.