Madekwe was born in London, England, and attended the Royal Academy of Dramatic Art in London where she gained a BA in acting. While attending the school, she appeared in numerous stage productions including King Henry V as Princess Katherine and Wuthering Heights as Catherine Earnshaw.

Madekwe started her acting career with a film entitled Storm Damage. Since then she has made guest appearances on Teachers, Doctors, Casualty, and Drop Dead Gorgeous. Madekwe landed her first motion picture in the Woody Allen film, Cassandra's Dream, opposite Colin Farrell and Ewan McGregor. Following that success, she played Elisha in the BBC Three drama pilot West 10 LDN, and appeared on six episodes of Trexx and Flipside as Ollie. In 2008, she landed the role of Bambi on popular ITV drama Secret Diary of a Call Girl which eventually was picked up by Showtime in the United States.

She is featured heavily in the third season. Madekwe starred in 2008's How to Lose Friends & Alienate People. Her other theatre credits include: Little Sweet Thing by Roy Williams, Flight Path by David Watson and many more.

Madekwe has a fashion blog "Ring My Bell" which has grown to be, as written by Look Magazine, one of the top fashion blogs. Ashley's blog contains entries about clothing, her career and her personal life. Madekwe's fashions has the focus of magazines such as Italian Vogue, Grazia, Asos Magazine, Heat, Pride and many more.

Madekwe made her official U.S. debut in the 2009 drama series The Beautiful Life which aired on The CW. She is currently appearing in the ABC series Revenge as a series regular.

In June 2012, Madekwe married her long-time boyfriend Iddo Goldberg

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