A 45-year-old man from Maesteg died in a collision on the A465 at Resolven near Neath, police say.
A white Renault articulated lorry vehicle crossed the central reservation and collided with a white Citroen van travelling on the opposite carriageway at around 3.40pm on Thursday.
The driver of the van was pronounced dead at the scene, while the van's passenger and lorry driver were taken to Morriston Hospital for treatment.
South Wales Police are appealing for anyone who witnessed the collision to contact them.
More top news
The temperature fell to -10C in Powys and there is a yellow 'be aware' warning of ice until 11.00am
In Rhianna's memory £50,000 will be used to expand a play area in Gnoll Country Park for both disabled and non-disabled children to enjoy.
A report to be published today will recommend how many more Assembly Members there should be