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It is confusing, the first time I needed to go there I had a hard time figuring it out.
The station is 9 miles from Chianciano Terme (on the other side of the A1 autostrada) and a mile and a half from the historic center of Chiusi.
This is a year old post about train stations....not car rental.
Google is your friend.
You can rent hire cars at Chiusi-Chianciano station. Hertz is 50 yards down the street, Avis some distance away but they'll pick you up if you give them train details, Europcar a 10 mins walk and finally a small local company, Aesse, immediately opposite the station. Note they work local hours so will be closed for lunch (approximately 13.00 – 16.00) on weekdays and I don’t believe any of them are open on Saturday afternoon or anytime Sunday but check specific websites for more.