Goulart was born on 23 October 1984, in Sao Carlos, Sao Paulo, Brazil. While shopping for groceries with her mother at age 14, a hairstylist suggested that she should become a model. She moved to the state capital, Sao Paulo, and started modeling, moving to France shortly afterwards to develop her career.
In 2005, Goulart appeared on the covers of the April edition of Marie Claire France and, in December, Vogue Brazil.
She first appeared in the Victoria's Secret Fashion Show in 2005, the year she was contracted as an Angel. She received a star on the Hollywood "Walk of Fame" prior to the Victoria's Secret Fashion Show 2007. Although she is no longer an Angel, Goulart walked in the 2005, 2006, 2007, 2008, 2009, 2010, 2011, 2012, 2013, 2014, 2015, and 2016 Victoria's Secret Fashion Shows.
In 2008, she replaced fellow Victoria's Secret Angel Alessandra Ambrosio as the face of A/X Armani Exchange and she was featured in three seasonal print campaigns for the label.
In 2010, Goulart appeared on the cover of the October issue for GQ Mexico, Vogue Brasil and appeared in a campaign for Avon. In the same year, she was voted the best international top model by the magazine Glamour Mexico.
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In 2011, Goulart appeared in the Sports Illustrated Swimsuit Issue. She can be seen in the spring/summer 2011 campaign for Dolce and Gabbana, the Pre-Fall 2011 campaign for Givenchy, Yamamay's 10th Anniversary Collection and the Fall/Winter 2011 campaign for DKNY Jeans. The same year, she ranked number 100 in FHM magazine's list of the 100 Sexiest Women In The World. She also appeared on one of the four covers of Elle Brasil.
In November 2012, she was recognised as "Fashion Personality of the Year" by the Brazilian magazine Isto é Gente, and she also appeared on the cover of Glamour Brazil in December 2012.
In February 2013 she appeared on the cover of one of the four issues of Vogue Brasil, together with Bette Franke, Magdalena Frackowiak, and Mirte Maas.
In mid-2013, she became the face of MAC Cosmetics Tropical Taboo range and she was photographed by Zee Nunes for the October edition of Vogue Brazil in an editorial entitled "Olympiada Fashion". Later that year she appeared in a campaign for Agua De Coco promoting its spring/summer 2014 beachwear collection.
She also appeared on the cover of GQ Portugal in December 2013, after she was elected as the magazine's "International Woman of the Year" in May of that year