Ambrosio is best known for her work with Victoria's Secret and was chosen as the first spokesmodel for the company's "PINK" line. Ambrosio is currently one of the Victoria's Secret Angels and has modeled for brands such as Next, Armani Exchange, Christian Dior, and Ralph Lauren.
Ambrosio serves as an ambassador for the National Multiple Sclerosis Society.
She has walked the catwalks for designers such as Prada, Chanel, and Oscar de la Renta.
By 2004, she was selected as the first spokesmodel for the Victoria's Secret "PINK" line. In 2005, she walked the Victoria's Secret Fashion Show runway wearing lingerie made entirely out of candy. In the 2008 edition of the Fashion Show, she walked the runway three months after giving birth to her first child, and opened the show the following year in 2009. The 2011 show saw her wearing the heaviest wings (30 lb) ever made for the show while pregnant with her second child. In 2012, Ambrosio was chosen to wear the "Fantasy Bra". The Floral Fantasy Bra, created by London Jewelers, features amethysts, rubies, sapphires and diamonds (including a 20-carat white diamond in the center), all set in rose and yellow gold, according to InStyle. There's also a matching belt adorned with more than 5,200 precious stones.