Product ranges at M&S will be showcased via the app through tips on high-street trends, lifestyle, food, fashion and technology.
A Samsung spokesman said the app was not transactional, but added that this was something that might feature in the future, "as Smart TVs continue to advance in technology and more people are becoming aware of it".
Up until now, Samsung Smart TV apps have predominantly involved partnerships with media companies.
Apps currently available via the Samsung Smart TV App store include BBC iPlayer, LoveFilm, Netflix, YouTube, Teletext Holidays, Rightmove, Thomson Local, Facebook and Twitter.
Susan Aubrey-Cound, director for new channels at M&S, said: "This app enables customers to discover more about our products and innovations from the comfort of their living rooms, whilst supporting our broader marketing channels."
Samsung claims that more than 10 million apps have already been downloaded from the Smart TV app store across the world, as consumers embrace the format.
A Smart Hub interface on the televisions allow viewers to open content from branded apps and the internet, while the television also allows people to connect wirelessly to other devices including smartphones, laptops and tablets.
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