South Wales Police have confirmed 27-year-old Gavin Carter is the second person who died in the Heads of The Valleys Road crash on Tuesday 15 October.
The father from the Tonyrefail area is one of two people who lost their lives following a collision on the A465.
The collision happened at around 4pm between Baverstocks and Hirwaun and involved two cars.
An investigation is being carried out on behalf of the Coroner.
Gavin's family said "he had a heart of gold".
Both families are receiving support from officers.
Police are appealing for information and witnesses who may have dash-cam or mobile footage of the collision.