Arrezzo or Montepulciano?

Will you have a car?
Where else will you stay while in Tuscany?

No car. Previous stop will be Pienza.

Very different places. Arezzo is a city of nearly 100K with an ancient central core ay the top of the hill and Montepulciano is a rural tiny hill town of about 13K. If you want the rural countryside Tuscany of film and photo Montepulciano is easily the winner. If you want to explore a city that is an interesting mix of modern life and shops blended with the ancient and while not nearly as spectacular as Siena is also way less touristy.

Arezzo is reachable by train while Montepulciano reasonably requires a car.

Hope that helps,
=Tod

How will you be getting to Pienza without a car and how are planning on continuing your trip from there two either of the other destinations?

=Tod

Montepulciano is extremely popular during the daytime which is the only time I have been there and that was in the offseason. It’s possible that it quiets down at night, but I would choose Arezzo and play it safe.

Same question as above
How will you get to Pienza without a car?

A bus runs between Siena and Pienza.

The same bus goes to Montepulciano, about 15 minutes from Pienza. Unless you want to experience the evening ambience of Montepulciano, do it as a day trip from Pienza. The bus runs early from Pienza.

Trains and buses go throughout Tuscany. You won’t have problems getting around, it just takes longer than driving yourself.

Another vote for Arezzo, although to be fair I haven’t been to Montepulciano. I spent 2 nights in Arezzo as a stop between Rome and Florence. It was a nice relaxing change between the two busy cities.