The service will add to content already available from Channel 4's own channels including E4, More4 and the main channel's own programming.
It is currently available to PC users and is expected to roll out on video-on-demand at a later date.
National Geographic Channel will run a pay-per-view service, with each programme costing viewers 99p. The channel broadcasts programmes including 'Into the Lost World' and 'Monsters of the Deep'.
A Channel 4 spokeswoman said: "We're very pleased with the service up until now, and we hope that there will be many deals of this nature."
Last week, Intel became the first advertiser to provide free content via Channel4's new 4oD service.The Intel-branded Video Lounge offers users free access to full-length Channel4 shows, streamable to their PC.
Users can download content including full-length episodes of Channel 4 programming including 'Big Brother', 'Desperate Housewives', 'Teachers' and 'Spaced'.
Intel will use the Video Lounge to target fans of certain TV shows online. With a combination of ad formats and targeted editorial placements throughout Channel4.com, Intel will be able to link through a wide audience and link users through to its own site.
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