The man, from Truro, died following the collision between a Toyota RAV4 and a Land Rover Defender on the A390 at Probus.
The emergency services were called to the crash at 11:00 GMT on Monday. The 65-year-old driver of the RAV4 suffered fatal injuries and died at the scene.
The A390 was closed at Probus while police investigated the incident.
Read more on this story as it develops throughout the day on our Local Live pages.
A 65-year-old motorist has died at the scene of a two-vehicle crash in Cornwall.