A 37-year-old man died near Tilshead this morning after a Volvo collided with a Mercedes on the A360 just before 7am.
The road was closed for more than seven hours while police investigated.
Police are appealing for witnesses to the accident in which a 55-year-old man from Bradford on Avon also received minor injuries.
The man who died came from Sussex and was declared dead at the scene after the silver Volvo V40 was in collision with a black Mercedes.
PC Gary Rosier, of Wiltshire Police's Roads Policing Unit, said: "We would like to speak with anyone who was in the area and may have witnessed the collision itself or either vehicle leading up to the incident."
Anyone with information is asked to call Wiltshire Police on 101, or Crimestoppers on 0800 555 111, where information can be left anonymously.
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