The incident occurred when passenger laden Tata Magic vehicle going towards Baharagora from Ghatsila collided with a speeding vehicle coming from opposite direction, police said.
Three persons were killed on the spot while six others suffered serious injuries, sources said adding that they were immediately rushed to a hospital in Baharagora.
However, one of the victim was succumbed to his injuries in course of treatment, sources said.
Meanwhile, the traffic on the national highway was disrupted for sometime before the police reached the spot to bring back to normal.