Two vehicles were involved in the smash on the A706 near Bathgate at around 1pm yesterday.
Lothian and Borders Fire and Rescue were called out to cut out a man aged around 60 who was trapped inside the van.
The car occupants were described as walking wounded.
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Hide AdTwo ambulances and a fast response unit attended before taking one man to Stirling Royal Infirmary with back and neck injuries and taking another to St John's Hospital in Livingston.
A spokesman for the Scottish Ambulance Service said: "We attended a two car road traffic accident where a van ended up in a tree.
"We treated one male for neck and back injuries and two walking wounded."