The soap couple, who play Debbie Dingle and David Metcalfe in the long-running ITV show, had a son called Buster in 2010.
A spokeswoman for the show said: "Charley Webb and Matthew Wolfenden have today confirmed that they have separated. They will remain friends and are focusing on their little boy."
The pair, who got engaged in 2009, are both expected to remain with the hit show which celebrated 40 years on air last year.
Matthew, who won reality show 'Dancing On Ice' in 2012, tweeted on Wednesday:
Thank you so much for all your lovely messages. Unfortunately these things happen, and it's very sad. Buster is our main priority always. X— Matthew Wolfenden (@MrMattWolfenden) August 7, 2013
Charley's brother, Jamie Lomas, is married to 'Coronation Street' star Kym Marsh and recently signed up to appear in 'EastEnders'.