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 (Paris, Russia, Turkey, Thailand, Singapore),Vogue(Portugal),Marie Claire(Italy, Hungary),Glamour Hungary,(Britain, Italy, Korea, Brazil, Argentina, Sweden, Serbia, Hungary),Allure,and Jealouse Magazine. Palvin has appeared in campaigns forArmani 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." Palvin is the face of Amazon Fashion and appeared on Express and Chaos advertising campaigns.
Her runway debut was for Prada during Milan Fashion Week in February 2010. Palvin has also walked forLouis 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 returned to the Victoria's Secret Fashion Show in 2018. In 2019, she became the first Hungarian Victoria's Secret Angel.
Palvin is often compared to Russian model Natalia Vodianova;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 Mossas her favorite models.