Under the deal, the pay-TV broadcaster will debut its first VOD service on Sky Anytime+, the broadband-enabled on-demand platform launched by Sky last October.
The company will also introduce HD variants of Watch, Dave and Alibi on the Sky platform, joining the already available Eden HD and Good Food HD. Sky viewers will get access to Watch HD and Dave HD in October, with Alibi HD due to go live in 2012.
UKTV's new VOD service will see titles such as Fawlty Towers, Doctor Who and Planet Earth become available in Sky Anytime+. UKTV will "cherry pick" all the best programming from its network, including a range of box sets to be refreshed on a monthly basis.
The launch has the added bonus for Sky of giving its subscribers on-demand access to a range of programming from the BBC archive, including Top Gear, Planet Earth and Rick Stein's French Odyssey, along with shows from other UKTV networks.
Sky and the BBC have so far failed to agree a deal to launch catch-up service BBC iPlayer on the satellite platform due to differing views on the syndication of video on-demand content.
UKTV's executive director of commercial Keith Porritt said: "We are thrilled to become Sky's largest partner supplier of HD channels with high definition versions of some of our leading channel brands, and it's tremendously satisfying to be finally launching ours first VOD service this autumn.
"UKTV's position in the market is so unique, that we're confident our HD and VOD offerings will really add value to Sky and their customers."
Sky's commercial director Rob Webster added: "We're delighted that UKTV is taking further advantage of Sky's platform innovation in HD, and will soon also be making its content available on demand via Sky Anytime+.
"Millions of Sky homes have embraced HD and now simply expect to see their favourite programmes in high definition, while Sky Anytime+ is really making its mark too. This is great news for Sky customers, driving yet more value into their Sky subscription."
Also today, Sky reported bumper pre-tax profits of £1 billion in the year to the end of June, as the satellite broadcaster announced a £750m share buy-back scheme to placate investors unhappy with the failed takeover bid by Rupert Murdoch's News Corporation.