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. She has also been featured on the covers of the British, Australian and Russian editions of Vogue and on the cover of Vogue Italia 5 times. Pivovarova appeared in the 2008 Pirelli Calendar. In December 2009, she became the face for Giorgio Armani.
She opened the spring show for Chanel couture in Paris in May 2008. In July 2008, she closed the fall show for Chanel couture in Paris and also walked for Jean Paul Gaultier couture. In January 2009, she walked the Christian Dior, Elie Saab,Chanel, Valentino couture shows in Paris. Her agencies are: Unique Models in Denmark, IMG Models in New York City, and Donna Models in Tokyo.