Modelling clothes, footwear and accessories for the back-to-school season, Rita was photographed at iconic London areas such as Buckingham Palace, Big Ben, the London Eye and inside a double decker bus, for the 'Material Girl Hits London' campaign.
The British songstress, who is dating DJ Calvin Harris, confirmed last month that she was to be the new face of Material Girl, which is inspired and designed by pop icon Madonna and her daughter Lourdes, aka Lola.
Madonna and Lola said: "Rita is a talented beauty, but what really drew us to her is the confidence she oozes through her music and her unique sense of style."
"On stage or off, in photos or on the street - she's a magnet! This is what the Material Girl brand is all about!," they continued.
Rita, 22, also shared some photos on her Instagram account last night (9 July), and shows her patriotic side as she stands behind London's famous gates of Buckingham Palace while posing in a solider's bearskin hat.
Doing the famous salute, Rita shows off her toned body and lace bra in a sheer black and white blouse. She said: "First look at my @MaterialGirl campaign. #yeaahhhh #herewego wooohoooo @madonna."
Last week, the 'Shine Ya Light' singer also showed off her eclectic mix of camouflage, glitter and jewelled nails from the range.
Rita, who has taken over from Georgia May Jagger to be the brand's new ambassador, quoted Madonna's famous lyrics from her song 'Material Girl'. She captioned the photo: "Cos we are living in a material World and I am your Material GIRL! @materialgirl."
Take a look at some behind-the-scenes photos of Rita's fashion shoot:
Copyright: Material GirlAlso check out Rita giving a tour of London and talking about her collaboration with Madonna and Lola: