From July, about 4,000 hours of archived content, including classics such as 'Queer As Folk' and 'Trigger Happy TV', as well as old episodes of shows like 'Grand Designs', will be added to the 4oD catch up service on Channel4.com.
The 4oD service currently allows internet users to view programmes for 30 days after they are broadcast, but Channel 4's decision to place archived content onto the site means viewers can watch the shows online at anytime.
However, some programmes such as US sitcom 'Friends' will not be available on Channel4.com due to rights or legal issues.
Jon Gisby, director of future media and technology at Channel 4, said: "We were the first broadcaster to launch a comprehensive video-on-demand service in 2006 and since that time 4oD has become one of the UK's most popular VOD brands.
"The addition of archived content to 4oD on channel4.com means we will be the only UK broadcaster to have all of our content available online.
The BBC currently shows programmes via its iPlayer service for only seven days after they air.
Channel 4's decision to add archived content on Channel4.com follows a relaunch of the site on April 1, which strengthened the 4oD service.
Due to its improved capabilities, the broadcaster has taken the decision to close the 4oD desktop application once all of the archived content is available via Channel4.com.
Gisby said: "We are extremely proud of the new and improved service and think the combination of fantastic content that's easy to find and view will prove a compelling service for all users."
In the first month since the re-launch, Channel 4 said it had seen a 111% increase in viewing compared to the previous month, with shows such as 'The Inbetweeners', 'Hollyoaks' and 'Come Dine With Me' performing particularly strongly.