The deal, which was brokered by the girl group's parent label, Universal Music UK, is likely to include promotional campaigns involving mobile media and MP3 tracks, but there are no specific details at present.
Samsung began its partnership with Girls Aloud earlier this year by sponsoring the Dublin leg of the group's 'Greatest Hits' tour.
Girls Aloud, who are signed to Polydor Records, already have a multimillion-pound tie up with Unilever hair care brand, Sunsilk. They promote the brand's in-store marketing and on-pack promotions, as well as appearing in a Sunsilk TV ad.
Band member Sarah Harding also has an existing deal with lingerie manufacturer Ultimo, and Cheryl Cole has fronted ad campaigns for Coke Zero.
Anthony Marsella, chief marketing officer at Samsung Electronics UK, said: "We wanted to work with an artist that could give us instant access to millions of homes in the UK and would also give us credibility with those audiences.
"We knew that we would need to approach a label partner that had both the vision and capabilities to recognise our needs and could understand the desired fit with our band."
Since being formed on the reality TV show 'Popstars the Rivals', Girls Aloud have notched up 13 consecutive top 10 singles, including 'Sound of the Underground', 'Love Machine' and 'Something Kinda Ooooh'. The band also released a joint single with Sugababes in aid of Comic Relief, and a cover of the Aerosmith and Run DMC classic 'Walk This Way', which went to number one in the UK chart.