James was previously married to his Shameless co-star, Anne-Marie Duff. The couple met in 2004 on the set of the British dramedy series, in which they portrayed love interests —and eventually husband and wife — Fiona and Steve McBride.

While together, James and Anne-Marie were notoriously private individuals.

In 2011, James told USA Today, "We've played it very cautiously ... It's who we are individually, and it's also a strategy. We respect the media, and we use it respectfully to sell movies and sell theater."

He added that he and Anne didn't "like going to parties or premieres if we're not involved. If my career isn't going that well, I'd rather it flounder than desperately trying to show up on red carpets: 'I'm for hire! Remember me!'"

In 2016, the former partners announced their divorce via a joint statement to USA Today.

"It is with tremendous sadness that we have come to the decision to divorce. ‎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."