The agreement, which is worth a reported £150m over five years, will ensure that all new HBO-commissioned shows and series will be broadcast first on Sky channels in high definition.
Sky's first exclusive HBO production will be Boardwalk Empire, a new Prohibition-era drama from Oscar-winning director Martin Scorsese and The Sopranos writer Terence Winter.
Starring Steve Buscemi, Michael Pitt and Kelly Macdonald, Boardwalk Empire will air on Sky shortly after its US premiere on HBO in September.
Under the deal, Sky will broadcast HBO's new fantasy drama Game of Thrones and the Dustin Hoffman-starring Luck after they have been aired in the US. It will also have first negotiation for rights to new series of established HBO shows and any future HBO UK co-productions.
The satellite broadcaster will further be able to offer access to archive HBO programmes such as The Wire, Curb Your Enthusiasm and The Sopranos on its on-demand platforms, including the forthcoming Anytime+ service.
"We are committed to bringing customers the best possible choice of pay content, whether that's through original UK production or the best of the US," said Sky managing director of entertainment, news & broadcast operations Sophie Turner Laing.
"Like HBO, we believe that innovative, high-quality content is worth paying for. We are therefore delighted to have partnered with one of the most renowned names in television. HBO has demonstrated year after year the opportunity for pay television to push creative boundaries and create must see TV."
HBO president of programming sales Charles Schreger added: "We are enormously encouraged by the ongoing success story of pay TV in the UK and Ireland and it makes sense for us strategically to find a partner who can sustain a real commitment to investing in content.
"We believe that Sky customers are in for a real treat with the spectacular shows currently in production such as Boardwalk Empire, as well as new seasons of established HBO favourites."
The deal follows Sky's recent broadcast of HBO's World War II epic The Pacific, in which it angered subscribers by only making the series available on Sky Movies.