Lima never thought about being a model, although she had won many beauty pageants in elementary school. However, she had a friend at school who wanted to enter a modeling contest and did not want to enter alone, so Lima entered with her. Both sent in pictures, and the contest sponsor soon asked Lima to come out for the competition. Soon after, at the age of 15, she entered and finished in first place in Ford's "Supermodel of Brazil" model search. She subsequently entered the 1996 Ford "Supermodel of the World" contest and finished in second place. Three years later, Lima moved to New York City and signed with Elite Model Management. After acquiring representation, Lima's modeling portfolio quickly began to expand, and she appeared in numerous international editions of Vogue and Marie Claire. As a runway model, she has walked the catwalks for designers such as Vera Wang, Giorgio Armani and Valentino, among others. Lima became a GUESS? girl in 2000, appearing in that year's fall ad campaign. She also appeared in the book A Second Decade of Guess? Images.
Lima continued to build upon her portfolio, doing more print work for Maybelline, for whom she worked as a spokesmodel from 2003 until 2009, the same year she appeared in the company's first calendar, a limited edition run also featuring Kemp Muhl, Jessica White, Julia Stegner, and Anna Wang. Lima has also worked for notable fashion brands bebe, Armani, Versace, BCBG and Louis Vuitton. She also appeared on the covers and in the editorials of other fashion magazines such as Harper's Bazaar, ELLE, GQ, Arena, Vogue, V, Esquire and French Revue des Modes. Her April 2006 GQ cover was the highest-selling issue that magazine for the year. She also appeared in the 2005 Pirelli Calendar and became the face of Italy's cell phone carrier, Telecom Italia Mobile, a move that earned her the nickname, "the Catherine Zeta-Jones of Italy."
In February 2008, Lima was featured on the cover of Esquire, re-creating the classic 1966 Angie Dickinson cover on Esquire's 75th anniversary along with fellow Victoria's Secret Angels Alessandra Ambrosio, Karolina Kurkova, Izabel Goulart and Selita Ebanks. She appeared only in shoes, diamonds and gloves for the November 2007 issue of Vanity Fair celebrating 20 years of supermodels with her fellow Angels. In February 2008, she was chosen to be the face of Mexico's Liverpool department store chain and launched the partnership with a press conference, runway show, and summer campaign. Lima returned to the high fashion runway in 2009, walking for Givenchy. That same year, after visiting Turkey, Lima signed a contract with Doritos to appear in print campaigns and commercials which began airing in Turkey that April. She was also one of the faces of Givenchy for the Fall/Winter 2009 season, alongside Mariacarla Boscono and Iris Strubegger. Lima is one of the two faces of Blumarine's Fall/Winter 2011 season.
In 2011, Lima signed a deal as a spokeswoman for Megacity by Votsu, a Brazilian social gaming company, to appear in their commercials. She also became the face of Brazilian luxury brand, Forum for there F/W and S/S seasons. Adriana Lima has worked with the most established photographers in fashion such as Inez van Lamsweerde and Vinoodh Matidin, Vincent Peters, Mario Sorrenti, Mert Alas and Marcus Piggott and David Sims.
In 2006, Lima ranked as the fifth highest paid supermodel. In 2007 and 2008, she ranked as the world's fourth highest paid supermodel by Forbes Magazine.