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A silver Mercedes C220, which was travelling west towards Wetherby town centre, had been involved in a collision with two pedestrians who were part of a group walking along the road in the same direction.
A 65-year-old man received emergency treatment at the scene but was pronounced dead a short time later.
A 52-year-old man was taken to hospital by air ambulance and remains in a critical condition.
The Mercedes driver, a 40-year-old man, was arrested on suspicion of causing death by dangerous driving. He was later released under investigation.
A road closure was put in place while the scene was examined and reopened shortly before 10pm.
Anyone who witnessed the collision or the circumstances leading up to it is asked to contact West Yorkshire Police Major Collision Enquiry Team via 101 quoting 13190563820.