A black Ford Fiesta and a black Renault Kadjar were involved in the collision on the B4278 between Penrhiwfer and Tonyrefail at 11:35 BST.
South Wales Police said the driver of the Fiesta suffered fatal injuries.
The 43-year-old female driver of the other vehicle was taken to hospital along with her three-year-old daughter.
The force said their injuries were not believed to be serious.
A 25-year-old man died following a road crash in Rhondda Cynon Taff on Friday.