Volterra to Montepulciano via train

Since it is nearly all are Regionale trains there is no advantage to purchasing tickets in advance on-line. I would buy the tickets in the station prior to departure. Options are somewhat limited. You best bet is the 8.40 with only three changes and just under six hours. You can determine the bus once you are there. Taxi costs would be reasonable for both situations.

It looks like you can get a bus at 8:00 that arrives at the station at 8:20. Plenty of time to get the 8:40 train Frank suggests.

Some sources recommend taking the trains only as far as Chiusi-Chianciano Terme as the bus service to Montepulciano is better from that larger station. You might ask your lodging host in Montepulciano for advice. Sometimes hosts will offer to pick you up....

Sir, that is not how you should travel to Montepulciano.
The Volterra Saline station has (infrequent) trains that can take you only to Cecina, on the coast, so basically the opposite way you intend to go.

First of all, you should seriously consider renting a car to visit that area (both Volterra and Montepulciano). Those are rural areas with quaint small towns which have infrequent bus service (or none at all on Sundays). Not having a car will seriously limit your ability to visit the region.

Having said that, the way you go from Volterra to Montepulciano using public transportation is convoluted, and it will take you about 6 hours, as opposed to only about 90 min if you drive a rental car.

First you'd take the 770 bus to Colle Val D'Elsa. Once in Colle Val D'Elsa you'd switch to the bus to Poggibonsi. At Poggibonsi you'd take the train to Siena, then in Siena you switch to the train to Chiusi-Chianciano. You can stop at the Montepulciano station if you want (which comes before the Chiusi station) but bus service to the actual town of Montepulciano is very infrequent, so you might be better off going to Chiusi, where there are more buses going to up Montepulciano.

RENT A CAR!

What Roberto Said!!!!!

The other advantage of renting a car is the ability to drive through some lovely countryside at your own pace.

I'd actually suggest making a day of it, which you would have to do by bus/train anyway, and drive from Volterra to San Gimignano. Spend a few hours there, then take the road from San Gimignano to Castillina in Chianti. SR 429 is a spectacular road up the mountain. At Castellina you'd catch a little of the famed SR222 going south. You could then take the SR2 on the outskirts of Siena, then catch SS223/SS73 and go either small roads through Asciano or SS715 to SP135.

We took a detailed map as well as a Garmin with the Italy/Greece card. If we ever go tired of wandering the countryside, we'd just key in our destination an let the Garmin guide us.

If you prefer to use public transit, the bus/train route recommended by Roberto is the much better option. I've taken the bus from Volterra and it's easy provided you're not traveling on a Sunday. In addition, the bus trip to Poggibonsi will only take about 2 hours versus around 4 hours by train, plus it avoids having to get to the Volterra-Saline train station (bus departs from piazza in Volterra). While Montepulciano train station is closer to the town than the Chiusi station, there's almost always a bus to Montepulciano waiting in front of the Chiusi station or one will arrive shortly.

Thank you everyone for your suggestions. You all have helped me so much! Yes, driving a car would be the easiest, however, I am partially visually impaired, so driving in a a foreign country would not fair well for me, and besides, driving the country side alone does not sound like much fun, so I think I will take the 770 bus to Colle Val D'Elsa, switch buses to Poggibonsi, take the train to Siena, switch trains in Siena going to Chiusi-Chianciano (skip the Montepulciano stop) and get off at Chiusi-Chianciano, and then take a bus to Montepulciano from there. Again, thank you all for your help - you all rock this traveling stuff!

Renting the car will be quicker. Depending on your budget you can also use a driver. I went from Volterra to Montalicino with a driver and we even stopped along the way a few times for wine and a little hamlet tour. Luca was great. http://hillsandroads.com/