The collision happened around 8:40 p.m on Saturday the St-Paul rural road.
The driver of the pickup truck was not injured.
However, the man and the woman in the other vehicle were pronounced dead a few hours later.
Lt. André Gagné of Saguenay police said the driver was arrested at the scene of the collision.
He will appear at a courthouse in Chicoutimi on Monday.
He is expected to face charges of impaired driving causing death.