He trained at the Guildhall School of Music and Drama where he was a contemporary of Dominic West and Daniel Evans and graduated in 1996.

[1] His credits include Band of Brothers, The Mother of Tears, Ancient Rome: The Rise and Fall of an Empire, Bonekickers, Henry VIII: The Mind of a Tyrant and a long running storyline in Casualty, as well as an episode of ITV2 drama Secret Diary of a Call Girl.

In 2009, James appeared in the Doctor Who episode "Planet of the Dead", co-starring with David Tennant, the pair having first worked together in Manchester's Royal Exchange Theatre 1999 production of King Lear.

James's other theatre work includes Blood and Gifts (2010) and Much Ado About Nothing (2011), alongside David Tennant and Catherine Tate.

In November 2015, he reprised his role as Prime Minister Mr Evans in King Charles III on Broadway, New York.