She is best known as the longest appearing fashion model for Prada, posed for 19 advertisement campaigns, a record Pivovarova has set for the brand.

[9] Pivovarova has appeared in advertisements for GIADA,[10] Prada, Chanel, Balenciaga, Dior Beauty, Miu Miu, Yves Saint Laurent, Mulberry, Chloé, Jimmy Choo, Max Mara, Hugo Boss, Giorgio Armani, Michael Kors, Lanvin, Juicy Couture, Etro, Frame Denim, H&M, Alberta Ferretti, Dsquared2, Massimo Dutti, Toteme, Shiseido, Pringle of Scotland, Paul & Joe, Longchamp, John Galliano, Biotherm, Kenzo, Thomas Wylde, Paco Rabanne Fragrance, Moncler, PHI, Olay, Mango.

[8] 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 one of the "World's Next Top Models".

[13] In December 2009, she became the face of Giorgio Armani and Mert Alas and Marcus Piggott photograph Pivovarova for Longchamp, alongside Kate Moss.

[16] Pivovarova made her acting debut in the 2011 science fiction thriller In Time, opposite Justin Timberlake and Amanda Seyfried.

Took her own self-portrait for the new Rag & Bone Do-It-Yourself ad campaign spring 2011 along with models Abbey Lee Kershaw and Lily Aldridge.

Pivovarova was on the cover of Vogue Italia for their June 2016 edition photographed by Mario Sorrenti,[22] she then appeared in the AD Campaign for Prada's Pre-Fall 2016 collection.

[11] In March 2007 a collection of Pivovarova's work including the portraits of Vlada Roslyakova and Snejana Onopka were displayed in Paris.

[14] They married in Thailand and recreated the scene for a photo shoot in the June 2009 edition of American Vogue with close family and friends, including Jessica Stam and Irina Kulikova.