Police said the crash happened at 07:10 on the B7066 Whitburn Link Road, near Polkemmet Country Park.
Several roads have been closed. They are due to open at 12:30.
The 58-year-old man who died was a driver in the stationary car.
The occupants of the van suffered minor injuries. Police are appealing for witnesses.
A man has died after a van crashed into a stationary car in West Lothian.