Deyn began working early, in the age of 13. She worked part-time, at a fish and chip shop in Ramsbottom. Since early age she had an eye for style; by 17 she had shaved her. "I’ve had short hair since I was 13, and when I was 17, I had a skinhead." She has won the Rossendale Free Press "Face of '99" competition, aged just 16 in 1999. Then moved to London, working in a fast-food restaurant during the day and a bar at night but admits: "It didn’t quite work." During that time she has also attended college in Hull, studying drama and music.
Deyn was spotted while shopping with fashion designer Henry Holland in Kentish Town, London. She has signed with SELECT model management while then changing her agency to Models 1 in the UK.
In May 2007, she was featured on the cover of Vogue, USA, together with Doutzen Kroes, Caroline Trentini, Jessica Stam, Raquel Zimmermann, Sasha Pivovarova, Hilary Rhoda, Coco Rocha, Chanel Iman, and Lily Donaldson as the new crop of supermodels.
She has also appeared on the covers of: UK Vogue, the Observer Woman supplement, The Sunday Times Style, Pop, Grazia, Time, Style & Life, Vogue Italia, and numerous other international publications.
Agyness Deyn has also worked with Anna Sui, Blugirl by Blumarine, Burberry, Cacharel, Gianfranco Ferré, Moussy, Maison Gilfy, Shiseido, Shiatzy Chen, Giorgio Armani, Mulberry, Paul Smith, Reebok and Vivienne Westwood.
Deyn was a guest editor of i-D magazine in May 2008. The issue devoted to her has included articles written by and about Deyn, as well as had featured interviews Agyness conducted with fashion insiders such as Vivienne Westwood.
In June 2009, the Daily Mirror reported that Deyn had quit modelling to spend more time with her boyfriend. A source told the newspaper that modelling became boring for Deyn and that she had hired an acting agent to pursue an acting career in British independent films.

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