James had early roles in television prgrammes such as Softly, Softly (1966); Love Thy Neighbour (1975); Quiller (1975); Gangsters (1976); Angels (1976); The Professionals; Out (miniseries) (1978); Minder (1979); Shoestring (1980) and The Gentle Touch (1984).
He was the first black actor to appear on the ITV soap opera Emmerdale Farm in 1972, teaching Seth Armstrong to read. However, he is best known for his role as Tony Carpenter in the BBC television soap opera EastEnders. James was one of the original cast members, appearing in the series from its debut in 1985 until 1987.
Other TV credits include: Casualty (1996), Lovejoy (1994), London's Burning (2002), Doctors (2002; 2005), The Bill (2006), The Line of Beauty (2006), Holby City (2006), Dream Team (2002), Afterlife (2005) and the television drama Angel Cake (2006). He also appeared in the 2005 Tim Burton adaptation of Charlie and the Chocolate Factory, where he played a shopkeeper.
In 2004 James played Herbert in Oxford Road: the Story, a radio play in which he worked alongside Dona Croll, an actress he had previously worked with on Elmina's Kitchen at the National Theatre. Elmina's Kitchen was adapted into a BBC Four televised film in 2005, in which James also starred.