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
George North is on course to return from injury when Wales resume their RBS 6 Nations campaign against Scotland on Saturday.
It's the Year of Legends, and Natural Resources Wales have picked its top 10 places to visit, to discover the myths behind some Welsh tales.
The average Welshman can expect health problems once he's 61, two years younger than the UK figure. For Welsh women, it's 18 months later.