The pair, who met on the set of British TV comedy Shameless, have released an official statement to share the news of their separation following nine years of marriage.
'It is with tremendous sadness that we have come to the decision to divorce,' the pair wrote in the joint statement they released.
Continuing they said: 'We enter this next phase with continued friendship, love and respect for one another and the shared focus of caring for our son.
'We ask that you respect our and, most importantly, our child's privacy during this time.'
James, 37, and Anne-Marie, 45 have a six-year-old little boy together called Brendan, who was born in 2010.
Known for keeping their private life out of the media, the pair got married back in October 2006 in a small and low-key ceremony celebrated among family and friends. Speaking about his wife shortly following their union James said she made him feel 'like myself a little bit more.'
The X-Men actor has previously spoken about their keenness for keeping their relationship away from the spotlight, telling the Washington Post: 'We don't talk about each other much and we don't turn up together at lots of events. We both really rejoice in having a normal life'
Anne-Marie has also previously spoken about the pair's romance, talking on Lorraine about her marriage last year she said, despite the pair's fame, 'It's dead easy to get on with your life. We're very lucky we are aware of our blessings. That helps to remind us to be good people.'
They started dating after they played on-screen couple Steve McBride and Fiona Gallagher in the gritty British comedy Shameless and have been together ever since.