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Discovered on the streets of Budapest at the age of 13, Palvin shot her first editorial in 2006 for Spur Magazine. Palvin subsequently moved to Asia where she maintained a steady stream of bookings. Since then, Palvin has been on the cover of L'Officiel (Paris, Russia, Turkey, Thailand, Singapore), Vogue (Portugal), Marie Claire (Italy, Hungary), Glamour Hungary , Elle (Britain, Italy, Korea, Brazil, Argentina, Sweden, Serbia, Hungary), Allure, Harper's Bazaar and Jalouse Magazine. Palvin has appeared in campaigns for Armani Exchange, H&M, Victoria's Secret, and Pull & Bear. In February 2012, she became an ambassador for L'Oréal Paris. In 2016, Palvin was revealed to be a part of the 2016 Sports Illustrated Swimsuit Rookie Class. She also became the new face of Armani's signature scent "Acqua di Gioia."

Her runway debut was as an exclusive for Prada during Milan Fashion Week in February 2010. Palvin has also walked for Louis Vuitton, Miu Miu, Nina Ricci, Emanuel Ungaro, Christopher Kane, Julien MacDonald, Jeremy Scott, Giles Deacon, Vivienne Westwood, Etro, and opened the pre-Fall 2011 Chanel show. In 2012, she walked in the Victoria's Secret Fashion Show and wore Rosa Clara on the Barcelona Bridal Week 2012 runway.

Palvin is often compared to Russian model Natalia Vodianova; British Vogue editor Miranda Almond said, "We chose Barbara because she is absolutely exquisite looking a cross between a young Brooke Shields and Natalia Vodianova". Palvin credits Vodianova and Kate Moss as her favorite models.

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Fruits Basket Magazine, the world's new leading men's magazine, gives guys what they want — beautiful women, jokes, sports, entertainment, gadgets, rides and beautiful women. Did we mention beautiful women?