Aoki was discovered in New York at a Rancid concert she had gatecrashed. She started modeling when she was 13, the same year Aoki was introduced to supermodel Kate Moss by her godmother who would later take the young Devon under her wing. It wasn’t much later that Devon signed onto Storm Model Management at the tender age of 14. In 1998, Devon replaced Naomi Campbell as the face of Versace.
She has modeled for the fashion houses Lancome, Chanel, and Versace. Aoki is 5 ft 6 in — an almost unheard of height for runway models, who are usually at least 5 ft 8 in tall. She has done ad campaigns for: Chanel Couture by Karl Lagerfeld, Versace Atelier by Steven Meisel, Junko Shimada by Bettina Kimenda and Baby Phat by Kimora Lee Simmons.