The Demand 5 app has launched in the Samsung Smart TV app store, where it joins services such as Netflix, LoveFilm and BBC iPlayer.
Users get on-demand access to a range of Channel 5 programmes, including Celebrity Big Brother, The Gadget Show, Home and Away, Neighbours and Benidorm ER, along with the Milkshake! children's strand.
Samsung operates one of the world's largest television app stores, with over 20 million apps downloaded worldwide on the platform to date.
Channel 5 head of digital media Paul Thornton-Jones said that bringing Demand 5 to Samsung TVs is "a key element of our strategy to make video on-demand services available for viewers across a broad range of connected devices".
"We've optimised the application to bring on-demand to the big screen, providing the best possible TV experience," he said.
Samsung UK's director of TV/AV Guy Kinnell added: "With Smart TV, Samsung is delivering more entertainment choices so consumers can catch up on their favourite programmes more quickly after broadcast.
"The launch of Demand 5 is a great addition to our platform and we're thrilled to provide our customers with the most complete catch-up services on offer."
The Demand 5 Player App is available on all 2011 and 2012 Samsung Smart TV models.