The incident took place on the N80 at Ravenswood, Bunclody when the man, who was on a motorbike, collided with a jeep at approximately 3.10pm on Saturday.
The man in his 50s was airlifted to St James' Hospital Dublin, the man in his 40s driving the jeep was not injured.
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The road was closed temporarily for Garda Forensic Collision Investigators to conduct an examination but has since been reopened.
Gardaí are appealing for anyone with information, particularly any road users who may have witnessed the collision or have dash-cam footage, to contact them at Carlow Garda Station on 059 913 6620, the Garda Confidential Line on 1800 666 111 or any Garda station.
