The tie-up sees the acting couple appear in a series of stylish black and white, romantic photographs for the British fashion house’s Trench Kisses Range. In one picture, the pair are shown kissing behind a Burberry bag.
A video, soundtracked by singer-songwriter Tom Odell’s version of “Hold Me”, is also being rolled out as part of the campaign.
The pair replace Romeo Beckham, who modelled Burberry’s Spring/Summer campaign, as the latest high-profile Brit to front the brand.
Christopher Bailey, Burberry chief creative officer, says: “This was a shoot full of love and laughter. It was such a treat to work with Sienna and Tom, and to capture their magic together.”
Burberry has used couples, albeit not real-life ones, in recent campaigns. The brand has previously paired actors Eddie Redmayne and Carla Delevingne as well as Rosie Huntingon-Whitely and Sam Riley.
The campaign, titled “A British Love Story”, launches in the Autumn.