Channel 4 is to offer a "catch-up" service for viewers by offering much of its programming online for 30 days after transmission for 99p per episode.
Current series such as Hollyoaks and Ramsay's Kitchen Nightmares will be available, alongside archived output from the network's 24 years on air.
The agreement covers all "homegrown" shows commissioned since June.
Each programme will "disappear" from users' computers 48 hours after they start to watch it.
It will be kept in a personalised library until it is first viewed, and then can be accessed an unlimited number of times during that two-day period.
Broadband deals
Channel 4 said it had signed contracts with nearly 100 independent production companies, including Endemol, which makes Big Brother, and will also offer selected films under the same terms at £1.99.
It promised that numerous classic series would be available when the service launches on 6 December, including dramas GBH, Teachers and Queer as Folk.
Peep Show, Spaced, Whose Line is it Anyway? and US import The Daily Show would be listed in its comedy line-up.
Factual programming from Jamie's School Dinners to property show Location, Location, Location were also part of the agreement.
Channel 4 has also announced a more restricted version of the deal for subscribers to BT Vision, a service offering TV via a broadband connection.
They will be able to see eight days of programmes, as well as films and classic material.
Last month the broadcaster signed a separate agreement with NTL Telewest to offer programmes on-demand through digital cable television.
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