Over 260km to la Spezia where most people take the train. Certainly not a day trip unless you want to spend about 6 hours in the car.
yes there is a car hire place at the railway station.
We have used Cortona as a base for 3 trips to Tuscany because we like the ambience of the town. We have explored from Florence to Assissi in Umbria. We drove the Chianti region, went to the flea market in Arezzo, dinner in Montepulciano. We stayed in a villa just outside of town so access was a little easier and we rented a car, of course.
I would agree that Tuscany is not suited to mass transport for touring. We saw so many things in the hills and on the back country roads. The signage is very good for driving.
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