The collision happened at 11:55 a.m. ET Friday on Highway 364.
Sgt. Gino Paré, who's with the provincial police, said one cyclist was hit from behind by the car and was thrown off of his bike.
The driver swerved, hitting another vehicle head-on, and the four other cyclists were hit in part of the secondary collision.
The road, a popular destination for cyclists, is about 100 kilometres northwest of Montreal.
Police said the winding road is lined by trees.
More to come