I plan to rent a car in Florence, then work my way through the Tuscan countryside. My route takes me through Lucca, Pisa, Volterra, San Gimignano, Siena, Pienza, and Montepulciano. Initially I planned to return the car in Florence then ride a train to Rome, but after looking at a map, this plan wastes time back tracking. Instead, would anyone know of a decent-sized town near Montepulciano, where I car drop off my rental car and also catch a train into Rome?
You may want to check Orvieto. A decent size town and may have a drop off place for your rental. We left our car at the Cortona-Camuchi train station during our 3 day visit to Rome, however we did not turn our car in because we had other places to visit after Rome. There was no charge for leaving the car at the Cortona-Camuchi train station and we were assured by the manager of our B&B in Cortona that the car would be safe there and it was. Orvieto is closer to Rome and may work for you to turn it in there.
Autoeurope lists Orvieto as having a pick-up/drop-off agency. There are plenty of trains into Rome with about a 80 minute trip.
I also suggest Orvieto.Its a 75 minute train ride into Rome and Orvieto is a nice town to explore or even stay overnight before traveling to Rome.
Another option would be to return the car to Chiusi. There are frequent trains between Chiusi and Rome.
I also suggest Orvieto. We are going to Italy in September and we are picking our car up in Pisa and dropping it off in Orvieto. The train from Orvieto to Roma only takes about 1 hour.
Orvieto really is the best bet.
We spent 2 weeks just driving around Tuscany and enjoyed exactly the areas you mention.
If interested, I have a photo-report on our time there by car, including the Carrara marble-hills area (where Michelangelo went to choose his marble) near Lucca.
Although this was a year ago I still have not uploaded Volterra yet but it's a very bustling hill town at night. I enjoyed it most in the daytime.
Samsn is correct. Chiusi is the closest place near Montepulciano to drop a car and train to Rome. Hertz is across the street from the station and Eurocar is about a block and a half away. It will take about half an hour to get there. Orvieto will take an hour and you will pass Chiusi on the way.
I also suggest Orvieto. We picked up our car from the rental at the bottom of the funicular. Do stop in and visit Orvieto. They have underground Etruscan caves and great food and accommodation. We also stayed in Montalcino and used it as our base when visiting in the area. It has alot less tourists. Also if you can squeeze it in, go to Assisi. It has stunning views and the basilica of St.Francis of Assisia is gorgeouus.