The former 'Dawson's Creek' star split from actress Heather McComb earlier this year and has now started legal proceedings to officially end their six-year marriage.
The papers were filed at a Los Angeles court and James cited "irreconcilable differences" as the reason for their break-up.
The pair tied the knot in Malibu in 2003, six months after the sixth and final season of 'Dawson's Creek' aired.
James' co-stars Michelle Williams and Busy Phillips attended the intimate ceremony.
Friends suspected a divorce was brewing when the couple sold their $2.5 million home in Studio City, California, in March.
They put the mansion - which features 180-degree canyon, mountain and city views, and a luxurious mist cooling system - on the market.
Since they tied the knot, James - who played Dawson Leery in the US teen drama - has guest starred in 'How I Met Your Mother', 'One Tree Hill', 'Ugly Betty' and 'Medium'.
Heather has appeared in 'Prison Break', 'Crossing Jordan' and 'CSI: New York'.
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