Goulart has stated that school was a particularly rough time, as she was made fun of for her skinny build, and was even called names such as "giraffe".

While shopping for groceries with her mother at age 14, a hairstylist suggested that she should become a model. She moved to the state's capital São Paulo and started modeling.

During Goulart's first ever fashion show appearance, she experienced a wardrobe malfunction. The unfortunate incident made many Brazilian newspapers and remains her most embarrassing moment. She was able to put her rocky start behind her and returned to the runway to model collections for A-list designers such as Bill Blass, Balenciaga, Bottega Veneta, Oscar de la Renta, Valentino, Jill Sander, Chanel, Michael Kors, Ralph Lauren and Stella McCartney, among many others.

She first appeared on the Victoria's Secret Fashion Show in the 2005 and made her Victoria's Secret Angels debut on 2006. She has also posed for photos with top photographers such as Terry Richardson, David Sims, Greg Kadel and Vincent Peters for such publications as French and Japanese Vogue, French magazine and Numero magazine. She also recently modelled in a photo shoot for Armani Exchange advertising their Lifestyle Spring campaign 2008.