Under the agreement between Samsung and Richard Desmond's Channel 5, a dedicated Five On Demand application will become available on Samsung's connected TV sets.
Samsung said that Five On Demand is the first of a range of new apps coming to its Smart TVs, including services from "broadcasters, retailers and holiday companies".
The apps join already available services from LoveFilm, BBC iPlayer, YouTube, Muzu.tv, PictureBox, Facebook, Twitter and the Tesco-owned Blinkbox.
Andy Griffiths, vice president of consumer electronics at Samsung UK, said: "Our new partnership with Channel 5 is the latest in our commitment to deliver unique new experiences to our consumers while maintaining Samsung's core values of industry-leading premium picture quality and revolutionary product design.
"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."
Five On Demand is already available online, as well as on YouTube, Sony's connected devices and the Virgin Media cable TV platform.