Before landing the role of Debbie, Webb previously appeared on the stage in Manchester in a production of Bugsy Malone when she was eight. She was nominated for Best Actress at the 2009 British Soap Awards and is nominated for Sexiest Female at the 2010 British Soap Awards.

Webb attended Philips High School in Bury. She has two older sisters and her older brother Jamie Lomas is also an actor, best known for previously playing Warren Fox on the Channel 4 soap Hollyoaks. Her younger sister Lucy Webb played baby Jon Dingle in the soap and her brother Daniel Webb played Aaron Livesy, Debbie's first cousin, in the soap.

Charley is currently dating Emmerdale co-star Matthew Wolfenden (David Metcalfe). In September 2009, they announced they were expecting their first child due in Spring 2010. Charley gave birth to a boy called Buster in April 2010.