The tie-up is the first time C4 has allowed sponsorship of its documentary programmes. The package includes 50 hours of shows on C4 and 52 hours on More4.
The car brand will use the sponsorship, which kicks off next month, to showcase its Passat model.
Daniel Hill, communications manager at Volkswagen (large cars), said: 'From researching our Passat audience we know that C4 documentaries are appointment-to-view programmes for them. This sponsorship allows us to align the Passat with intelligent content and position the model as the intelligent choice.'
The sponsorship deal includes programmes both from established and fresh documentary strands, such as Cutting Edge and More 4's True Stories.
The package will also incorporate single documentary strands including Love, Sex and Marriage - a three-part series from documentary maker Jane Treays.
Other shows include Medicine Man, a four-part series examining whether Western medicine is always superior to traditional alternatives.
Activity for VW across C4's on-demand platform 4oD will comprise 10-second pre-rolls and 10-second mid-rolls on 30-day catch-up documentary shows.
Volkswagen will also have a permanent branded documentaries section and branding on individual pages on 4oD. Clickable idents will take users to a sponsored
microsite on Channel 4.com as well as a competition area, and the marque will run ads across the C4 website.
The deal was negotiated by SponsorCom. Creative for the campaign was developed by DDB and Tribal DDB.