Florence to Montepulciano by car

1. Yes I would, because a car will be useful while you stay in Montepulciano to take day trips to the many small towns in the area. Bus service is limited. If you go from Florence to Montepulciano via the fastest way (i.e. with the A1 freeway to the Valdichiana exit, south of Arezzo) the photo opportunities are limited along the way. But a car is a good idea regardless, once you are in the Montepulciano area. You can also get there through a longer route, if you are not in a hurry. For example via the Chianti Road SR222 via Siena. It will take you 3 hours instead of 1.5, but if scenery along the way is important to you , it's a route to consider.

2. I would. You don't need to return the car in Naples. You can keep it if you want (although parking in Positano is expensive) or otherwise it would be best to return it in Sorrento, and take the bus from there. Or even better go to Positano, drop your bags, then drive to Sorrento to return the car and make it back to Positano by bus.

3. Yes, and also nearby Montalcino. Also the Chianti road mentioned above goes through a major wine producing area.

4. others will chime in. I have no suggestions to make.

Q4: I stayed at Meuble il Riccio and really enjoyed it. It's located within the city walls, close to a lot of the upper-town sights and restaurants, and they offer free parking a short walk away. Breakfast is extra, and I usually don't opt for breakfasts that are an extra €8, but it was fantastic. Try it the first morning and then decide whether to continue.

Thanks for the great insight!

Can you give us an idea of how you plan to divide your nights in each place? You have a lot of area to cover. Is your total trip 15 days which equals 13 nights? Or 13 days=11 nights.

This is how our trip is broken down: 2 nights in Venice; 2 nights in Florence; 1 night in Montepulciano; 4 nights in Positano; 3 nights in Rome.

You have a fast start, but a semi relaxing end.
To maximize the Tuscany portion, do as Roberto says and connect Florence and Montepulciano with the SR 222
Though it takes twice the time you won't be disappointed.

I'd drive to Positano, in October, you won't run into heavy traffic on the coast road.
Decide if you want to keep the car when you get there. A car will make it easier to reach Naples, then catch the train to Rome. If you don't want to drop the car at the station, drop it at the airport and take the Alibus into Naples Centrale.

In 2014, we rented a car in downtown Florence and drove to Montepulciano, avoiding highways. It was a memorable drive, we took our time, and had a wonderful lunch in one of the hillside towns. We got excellent driving directions from a poster on another message board, keeping in mind that the routes are not really marked with numbers. It is more a directional type instructions: take the turn for XYZ town, then head towards ABC town, etc. Although we had a great map, the road signs did not use the number system, just town names. If you want, I can find and post those exact directions for you here :) We dined at a wonderful outdoor restaurant, called Bar-Ucci in the town high in the hills, called Volpaiia. I suggest you make this your lunch stop!

Check out the Politian Apartments in Montepulciano, highly recommend! We booked an apartment in "the Annex" because the main house (attached) was booked. Amazing, with antique furnishings and all the comforts of Italian home life!

P.S. The road is curvy and we took our time, about five hours including lunch and a couple of oh-no-we're-lost-corrections. By the time we got to Montepulciano, I, the passenger/navigator, was a bit queasy. Next time I'd share some of the driving in order to avoid this.

http://www.bar-ucci.it/barucci.php

https://www.politian.com/en/