ellenem

emtravels123, All will depend upon your arrival time and day and whether the best car rental location for you is open. The car rental at the airport probably has the best hour, but check carefully the hours at small town locations. Chiusi is a town on the train line where some people rent a car—it's quite close to Montalcino. Again, check opening and closing times carefully.

bobthenavigator

The drive time from Chiusi Scalo to Montalcino is at least an hour. But, a pretty drive. Your other options are Orvieto and Grosetto, but do check the open hours.