Advice on Tuscany - where to stay, tours, etc...

The area you're talking about staying is just a short drive south of Florence. Montepulciano is one of many great hilltowns in the area that you can stay in.
And Florence is just a 1 hour drive south of Bologna.
Just pick a town, and go to Booking.com or other websites to find agriturismo accommodations. Virtually every farm in the area has apartments and rooms for rent as a secondary source of income, so there is not a lack of places to stay.
You say you're driving to Venice after staying in Tuscany. You go back up to Bologna and turn east, and it's a very easy drive from there. From Florence to Venice is about 150 miles, so it goes along pretty quick. I just caution you about the radar/cameras going over to Venice from the mainland.

I haven't driven in Europe, but I believe you need to be very careful about ZTLs (no-drive zones) in Bologna. I remember some head-clutching by a hotel receptionist when the American family in front of me at the counter said it had been driving around the city for a couple of days without realizing there were streets that are not to be driven on. You could see the expectation of €€€ traffic fines flitting across the face of the receptionist.

Stay either in Chianti or Montepulciano,Pienza and you will be in a perfect place. There are so many wineries. Why do you need a tour? We just followed signs and drove dirt roads to several wineries in Chianti. Little English was spoken but we had tastings and purchased wines. Fun experiences.
If your hotel is in a ZLT, they will send your license plate info to the local police so you won't get a ticket. We parked right in the center of Bologna's historic district without a problem as our hotel did that for us.
I would get the car as you leave Bologna and keep it until you get to Venice so you won't have to schlep your bags off and on trains.

Last month, we stayed at https://www.agriturismohumile.com/en/. It was located about 15 minutes outside Montepulciano. Beautiful farm with a pool, and immaculate rooms. We stayed for 5 nights but not sure about minimum night requirements in the summer. The area is beautiful, you can connect to Rick’s Heart of Tuscany Drive from here. We arrived by train at the Chiusi train station. Hertz is half a block to the right once you exit the station. Pick up and return was smooth and easy. There is also an Avis a little further away. The farm was 20 minutes from the train station. You can then take the train to Venice from Chiusi.

If you are going to be driving in Italy, each driver must have an International Driver's Permit, available at any AAA office for $20.

Hello Emily! My husband and I are also in our early 30s and we did a 2 1/2 weeks in Italy (Tuscany, Cinque Terre, and Rome) last year. Like you, we really wanted to see historically sights, quaint towns, and most importantly, small-scale family wineries. I would highly recommend Tours by Roberto. He's on all of the Rick Steves Tuscany episodes and absolutely fantastic. We did a total of three, yes three tours with Roberto and enjoyed great wine and amazing meals on his tours. Happy travels :-)

Hi Emily,

My family, friends, and I stayed in Tuscany this past June. We stayed in a B&B 20km north of Siena which was a great base to explore. We rented a minivan (which is a bit large for Italian parking spaces, but necessary for the size of our group). Driving in the Tuscany region was really straightforward. As others mentioned, you will need an International Drivers License (for each driver) and can get at AAA.

Here are a few recommendations from our travels:

• Borgo Argenina: http://www.borgoargenina.it. This is not an agriturismo, but a lovingly restored Tuscan B&B with two private villas (with fully appointed kitchens) and a main house. The owner, Elena, is a gracious hostess and is happy to make any arrangements for tours, winery tastings, and local restaurants. We reserved for just 4 nights. The highlight was the cooking class that she holds at the B&B in her Tuscan kitchen. It is in the evening, so you can come back after a day of touring to make your meal. We loved it so much that this weekend, we had our own “cooking class” at our house.
• Castillo de Verrazano: http://www.verrazzano.com. This is a winery and an agriturismo. Located in the heart of Chianti, it has one of the best tours and lunches I have taken anywhere. The lunch itself is spectacular (and you won’t need dinner later), from the house-made charcuterie to the spit roasted pork, everything was delicious.
• Tuscan Hot Springs: we spend a relaxing day in Bagno Vignoni to explore the small town, hike, and relax in the natural hot springs. Some of our group took spa treatments. Tuscan has a wide variety of hot springs (many free). Here is a link: https://www.discovertuscany.com/what-to-do-in-tuscany/thermal-baths/hot-water-spring-spas.html.
• Truffles: Elena arranged a lovely dinner for us in Monte at the restaurant of a local truffle hunter. For 39 Euros per person, we had a five course meal with an abundance of truffles and local Chianti wine. This truffle hunter also has tours (see Borgo Argenina site for details).

Enjoy your trip,
Sandy

Hi Emily,

Since you have not driven in Italy, this site will answer all your questions about ZTLs. In their PDF all other relevant info. Signage, speed limits and all other rules of the road. Being well informed will eliminate any surprise expensive tickets, sometimes up to a year, after your return.

https://www.italybeyondtheobvious.com/dont-mess-with-ztl-zones

Renting your car in Bologna and returning in Venice will make it much easier and in your case faster changing locations.

We have a favorite place in Tuscany that we keep returning to. It's extremely central to the places you mention. Nothing is over an hour away. It's been in Fortunatos' family for over 300 years but it took Gisella to turn it into what it is today. They are exceptional hosts who treat you as family.
They do rent mid season by the night.

http://www.borgorapale.it

Take the time to read their PDF. It covers restaurants, day trips, maps, wineries (spot on in this category) hiking biking. The list goes on and on.

I will second Vernazzzo and it's neighbor

https://www.vignamaggio.com/en/tuscan-food-and-wine-tours

http://www.toursbyroberto.com

Does a fine job of presenting the different areas of Tuscany and it's wines. We have just decided we can cover much more ground on our own but it requires more research. If we find a place we want to stay longer, it's up to us.

Do keep in mind the alcohol limit in Italy is much lower than here. Our solution is a DD and purchasing wine to take home or for an evening on the terrace.

Whatever you decide, you'll love this area of Italy.

My wife and I just returned from Tuscany. We stayed just outside Montepulciano at Villa Nottola, it was a great base for us. Good location, friendly staff and the on-site restaurant was suburb and reasonably priced. The restaurant saved us from driving the windy, dark roads at night to get back to a town for dinner.

From Montepulciano it was a reasonable drive to our favorite Tuscan towns - Volterra and San Gimignano, Cortona, Montepulciano and don't miss tiny Montecchiello and San Quirico d'Orca.
As for where to get your car, one thought I had is that as far as I know the rental car places in Florence are not near train stations and many of the smaller towns do not have rental car places either. Bologna may be the easiest bet.

Thank you all for your wonderful suggestions! I’ll be looking into the lodging/tour recommendations and appreciate the advice on driving and ZTLs.