Dyfed Powys Police are appealing for witnesses
The crash happened at around 2335 GMT on Betws Road in Ammanford. Dyfed Powys Police said an investigation had begun and the Independent Police Complaints Commission (IPCC) had been informed.
The man's next of kin were still being contacted. Police are also appealing for witnesses to contact Ammanford police station on 0845 330 2000.
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