The incident happened on the B981 between Cluny and Cardenden in Fife at around 6.45am today.
A 36-year-old man died as a result of the incident, Police Scotland said.
He is believed to have been the driver of the car.
Two men who were in the van suffered minor injuries and were taken to Victoria Hospital in Kirkcaldy.
Anyone who witnessed the crash is asked to contact police on 101.