BBC shows including Life on Mars and Little Britain have been made available to download from digital store iTunes.
Ashes to Ashes is among the shows that will be available for download
The deal makes the BBC the first UK broadcaster to offer programmes via Apple's download service.
Torchwood and Spooks are among the other shows that can now be purchased for £1.89 an episode in the UK.
Recently-aired programmes like Ashes to Ashes will appear on iTunes after they have been made available to view on the BBC's free iPlayer catch-up service.
The iPlayer is proving extremely popular, with more than 3.5 million shows streamed or downloaded in its first two weeks of operation after its Christmas Day launch.
"We want to give audiences a wide variety of options on how and where to view their favourite BBC shows," BBC Worldwide's Simon Danker said.
"With more people now choosing to watch TV shows on their iPods, fans can now enjoy those shows wherever they are."
Making shows available on iTunes was key to BBC Worldwide's aim of getting content out to the broadest possible audience, the corporation said.
The BBC is also planning to launch a joint on-demand content service with ITV and Channel 4 later this year.