Aoki was born in New York City and grew up in California and London, attending highschool at The American School in London. Her Japanese American father, Rocky Aoki, a former Olympic wrestler, is the owner and founder of the Benihana restaurant chain. Her mother, Pamela Hilburger, is a jewellery designer of German and English heritage.
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. Moss pushed for Aoki to be signed, and she was signed onto Storm Model Management at age 14.
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