Chatham-Kent OPP are investigating a serious crash near the Orford Road exit that occurred in the eastbound lanes of Highway 401 around 2:30 a.m. Monday.
Provincial police said a cargo van rolled into a ditch after colliding with a tractor-trailer.
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Emergency services responded and the lone occupant of the van was rushed to a local hospital with life-threatening injuries, OPP said.
A traffic reconstructionist from the West Region traffic incident management enforcement team is helping investigate the cause of the collision.
The investigation is in its early stages, police said.
Chatham-Kent provincial police is asking anyone that may have witnessed this collision to please call 1-888-310-1122.