I need help!!

Where are you staying overnight?

Not booked yet, that is why I’m panicking. Was thinking around Pienza for 2 nights and then another two nights in a different destination.

First day en route to Siena you could take the SR222 Via Chiantigiana (Chianti Road). Takes almost 2 hours without pit stops, so double the time since I am sure you will stop even just for photos.

Try to be in Siena at least half day to see the main Piazza del Campo, the Duomo, and maybe the Museo Civico inside the Palazzo Publico, on Piazza del Campo. The Museum closes at 7pm but last entry is at 6pm, so do that first.

After Siena drive to the accommodations near Montepulciano/Pienza. Stay the first two nights there. The next day visit Montepulciano, Pianza, Monticchiello. I don’t know if you have time for more, but in that area there is also Montalcino, Bagno Vignoni, San Quirico, Buonconvento, if you have time.

After the second night head to Saturnia for two nights. While there you can visit Pitigliano, Montemerano, Cascate del Mulino, maybe Sorana and Sovano (on the way to Pitigliano). It’s probably too much for one day, so you might have to make choices.

I can’t suggest places to stay in Montepulciano because it’s close enough to my country house near Arezzo, so I usually visit on day trips. Saturnia is in Maremma, so considerably further down in southern Tuscany (probably over 2 hours from Pienza). I’ve stayed in several places in Maremma, but the place I liked the best in Saturnia was this:
https://maps.app.goo.gl/FngMwKysqrhhowYA6?g_st=ic

When there I liked this nearby restaurant for traditional Maremma cuisine.
https://maps.app.goo.gl/Uo4fK914mv8sQtZn7?g_st=ic

The hotel above has a restaurant also, where they serve the free breakfast. It’s a bit fancy and they prepare a more innovative Maremma cuisine at lunch and dinner, but I usually prefer traditional food. I have enough of those innovative dishes that please the eye but don’t fill the stomach.

I suggest you look immediately for lodgings before making any further plans
Finding a place just 2 days from now near Pienza or anywhere in that area with parking is going to be a problem

Do you have your IDP? Required by law and rental agencies can/do ask
They can deny the rental if you don’t have

Make sure you understand ZTL restrictions and how to get out of Florence safely (without violations)

Try these
https://www.a440intuscany.com/
https://www.hotelcorsignano.it/

To add to Christine’s, make sure you know the rules of the road in Italy:

https://en.wikipedia.org/wiki/Road_signs_in_Italy
https://www.autoeurope.com/italy-ztl-zones/
And use Waze as your navigator as it is the best to warn you about police road checks hidden speed cameras (ubiquitous in Italy)

I hope you got your International Driving Permit before you left. It’s mandatory in Italy (rarely requested by the rental agent but required in case of police stop. The fine is 408€ for not carrying one).

Missing San Gimignano

Just checked Booking.com for Pienza for a day out. There are definitely nice places available. They ars not necessarily chee cheap. We have found many of our favorite places through desperate feeling searches at the last moment.

San Gimignano (and/or Monteriggioni) on the way to Siena are certainly other options that you can do in lieu of the Chianti Road. Or maybe you can do a bit of both. For example one could do the Chianti Road down to Castellina, then from Castellina descend to San Gimignano (less than one hour)
The issue is that there are only so many hours in a day, and doing Chianti Road, San Gimignano, Siena all in a day is quite a bit to chew (and a lot of driving in curvy roads).

Your choice

Thank you for all the information & travel tips. It has definitely given us more insight to the area & how to navigate it in the time we have here. Italy is absolutely beautiful & we are looking forward to the next few days.

Check with the agriturismo La Bruciata just 2 km outside Montepulciano. Perfect location to explore all the Val d’Orcia without having to change locations. We were there a week and I’d go back in a heartbeat. Hoping she has an opening for you.