As an art history student at the Russian University for the Humanities, Pivovarova never dreamed of becoming a model until friend and photographer Igor Vishnyakov took photos of her in 2005 and gave them to international modeling agency IMG, thus beginning her career. After signing with IMG, her first runway show was for Prada, who then signed her to a three-year exclusive advertising contract.

In the May 2007 issue of American Vogue she was featured on the cover with Doutzen Kroes, Caroline Trentini, Raquel Zimmermann, Jessica Stam, Agyness Deyn, Coco Rocha, Hilary Rhoda, Chanel Iman, and Lily Donaldson as the new crop of “supermodels,” and in her interview, she talked about her love for art and reading.