Favorite smaller Tuscany towns

Check out Volterra.

We stayed in Montepulciano and loved it. Would have also loved staying in Pienza and Montalcino.

We loved Montalcino. Spent a day hiking from there, visiting the abbey of Sant'Antimo, and a day driving to Pienza and Montepulciano wiht a stop also in San Quirico d'Orcia. There is a fabulous B&B there http://www.montalcinoitaly.com/home_cesira.htm, which was worth the trip. It's a quiet town, great place to call home temporarily. Monte Oliveto Maggiore (abbey) and many other quaint towns accessible from here.

Thanks so much for the great suggestions. All of these smaller towns fit the kind of experience we are hoping for I think. The other town that has popped up is Casole d' Elsa although I have heard it maybe a little too modern. Has anyone been there? Again, we really appreciate all of your help!

Volterra, while interesting (great Roman theatre just outside the town walls, plus a very good Etruscan museum), is a bit out of the way for visiting the rest of Tuscany. For southern Tuscany, Montepulciano or Montalcino (especially if you like Brunello wine) or Pienza are good smaller towns. San Gimignano if you want something a little further north. It's packed with day-trip tourists during the day, but is delightfully quiet in the evenings. Wouldn't the town in Tuscany fit your request for a village between the CInque Terre and Rome?