The deal gives Samsung Smart TV users access to Channel 5's on-demand service, and the group is expected to make an additional series of announcements throughout the week.
Samsung's Smart TV has already developed apps for LoveFilm, BBC iPlayer, YouTube, Tesco-owned Blinkbox, Muzu.tv, PictureBox, Facebook and Twitter, and claims to have the largest range of apps for IPTVs.
C5 has already done a deal with Sony for their IPTV and Blu-Rays.
Andy Griffiths, vice-president of consumer electronics, Samsung UK said: "With Smart TV, Samsung is delivering more entertainment choices so consumers can ‘watch’, ‘chat’, ‘surf’, and ‘share’ with greater possibilities and ease of use.
"By leading the development of the new Smart TV category in the UK, Samsung will once again transform the TV-viewing experience to the benefit of consumers, developers and retailers."
Rival Sony is pushing its internet-connected TV offering with an international campaign already running in the Asia-Pacific region.
Separately, the YouView consortium of UK broadcasters and ISPs is developing a standard for internet-connected TV delivery, but its launch has been put back to 2012.