ITV has made more than 260 hours of archive programmes ranging from Brideshead Revisited to Captain Scarlet available for sale on Apple's iTunes store.
The deal with Apple is the latest move to cater for the burgeoning popularity of on-demand television, and follows the BBC's announcement in February that it would sell programmes on iTunes.
Viewers can download whole series – prices per episode start at £1.89 – and watch them at their leisure on their computers, iPods or iPhones.
Newly released on the iTunes service are the ITV favourites Brideshead Revisited, broadcast in 1981 and starring Anthony Andrews, Jeremy Irons and Laurence Olivier, the 1999 John Thaw drama Goodnight Mr Tom, and Cold Feet, which began with a pilot in 1997 and ran to 32 episodes, featuring James Nesbitt and Helen Baxendale. Also available are the 1960s Gerry Anderson puppet drama Captain Scarlet and the Inspector Morse spin-off, Lewis.
Later this year, Inspector Morse, The Prisoner, The Saint and adaptations of Jane Austen's Emma and Northanger Abbey will be made available. Current shows will not be put on iTunes, although more recent programmes may become available 30 days after they have been broadcast.
Already available on iTunes are the BBC's Life On Mars and Torchwood, and Channel 4's Shameless and Skins.
The ITV deal was brokered by Granada Ventures, which is part of ITV Worldwide and has already made more than 300 films from the broadcaster's DVD catalogue available on download sites such as lovefilm.com. Dawn Airey, the managing director of ITV global content, said: "ITV has thousands of hours of classic content in the archive which we are bringing to a whole new audience via iTunes.
"We want to give our viewers the opportunity to watch their favourite shows wherever they are. Our strategy is to deliver 360-degree value for our content on multiple platforms, and in multiple territories."
ITV's move reflects a desire from viewers to be able to watch what they want, when they want. The BBC, ITV and Channel 4 already have their own on-demand services – BBC iPlayer, ITV.com and Channel 4oD.
More than 2.2 million people used the iPlayer, which allows viewers to watch BBC programmes up to seven days after they were transmitted, in the three months following its launch at Christmas. ITV.com hit a peak of 2.2 million viewers in November last year.
The two channels, along with Channel 4, are also collaborating on a new, online, catch-up service provisionally named the Kangaroo Project, which is due to go live later this year.