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
A 110-year-old All Blacks rugby shirt has sold for £180,000 at auction in Cardiff. We've been taking a look at what else you could buy...
As Super Saturday approaches it's not just us that are preparing to get behind Team Wales. Our pets are getting in the spirit too!
A 'duck lane' has been put in place beside a canal in Brecon to encourage people to be more considerate when walking the towpath.