An 11-year-old girl remains critically ill in hospital after the head-on collision on the A48 near Margam.
A 39-year-old woman and a man, 61, also died when a blue Rover 75 and a silver Mondeo crashed at around 1600 BST on Wednesday.
The 11-year-old, who is related to the woman and four-year-old child, is being treated at Morriston Hospital, Swansea.
Police have said that the 61-year-old man who died was travelling in the Rover car which collided with the Mondeo in which the three other victims were travelling.
The accident closed the road between Margam village and the junction of the B4283 Water Street.
South Wales Police have appealed for witnesses to the collision or who saw how the cars were being driven prior to the crash to contact them.
Anyone with information is urged to contact the roads policing unit on 01792 456999 or their local police station.
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