Four occupants of the car, including a young couple, were killed on the spot while the driver of the vehicle succumbed to injuries at a hospital later.
They were returning to neighbouring Salem after a pilgrimage to Kumbakonam while the occupants of the van were proceeding from here to Tiruchirappalli on a vacation tour when the mishap occurred at Kuppampalayam, Superintendent of Police S R Senthilkumar said.
Nine injured persons were undergoing treatment at a private hospital here.