My family party of six was in trouble, having unexpectedly left a horrible rental in Tuscany earlier in the day, with no place to stay. We took a chance and drove to Volterra, and then (using the Rick Steves guide) contacted the Albergo Etruria, where they were kind enough to rent us three rooms at the last minute. Later, after we had fallen in love with the town, they allowed us to extend our stay without problem.
The hotel is not fancy, some of the rooms are small, and the lack of air conditioning was a little uncomfortable given the hot weather we were experiencing. However, all of this was made up for by the overall warm hospitality of the managers and their staff. The rooms were otherwise comfortable, clean, and nicely decorated. There is a lovely dining room where a very nice breakfast is served (included in the rate) each morning; my wife, a strict coffee snob, gave the cappuccino two thumbs up! There is a common area on the first floor that has a refrigerator, stove, and microwave for use by the guests, as well as a computer and TV. Best of all, there is a rooftop garden area that is both expansive and beautiful.
Really, though, the staff makes the experience! They were all helpful to a fault, whether printing up our train e-tickets, giving us six Wi-fi passwords every day for our use, or dealing with pretty much any other request we made.
And the price on the rooms is extremely reasonable.

What this hotel has lacking, limited hot water, small bathroom, it makes up for in the caring of amazing hostesses Lisa and Josephina. We went there for our Volterran wedding and were treated like royalty. They helped make our wedding a fairytale come true. Lisa could not do enough for us.
What this hotel does have is a huge varied breakfast, with Lisa at that ready to fresh brew any coffee of your choice, a central location to explore the quaintness of Volterra, a lovely roof garden with a wonderful view, a roof garden room which we were lucky enough to book (highly recommended), wi-fi and a computer to use in a nice library/ sitting room, and of course a staff that take pride in making you happy. You can book direct for good pricing.

We stayed here for a couple of nights and had a window overlooking the street. The town is amazing and the location couldnt get any more authentic. The people were nice and breakfast was very tasty. We did not know there was an outdoor space until reading this later.

I would reccomend this hotel to friends and definitely reccomend Volterra to everyone.

...but, "it is an old building". We heard that on several occasions when we asked about heating for the room, water pressure in the shower and spotty wifi access. The hotel is in a great location, right in the middle of the city and close to the pay parking lot (add 11 euros to your budget if you park in the garage).The room was large and clean with a small balcony. The rooftop terrace was very nice but unfortunately for us, it was windy and rainy on our visit. Breakfast was typical with cut meats, pastries, juices, coffee and tea. One of the ladies at reception was very nice and helpful and English was no barrier for communication.

But, remember It is an old building and set your expectations accordingly. There is no lift, the bathroom is small (the shower smaller), the furnishings are worn and the water pressure in the shower was terrible (although the bidet had great flow). The heat (like the airconditioning) is apparently controlled by the city and we hit an unseasonably cold streak in April. We hadn't been warned that there would only be heat from 6 pm to 10 pm which would have been helpful information. If you rely on wi-fi, you might be disappointed in the signal quality.

Volterra is really a neat city to visit and this hotel puts you right in the middle of it, but it is in an old building.