Pitigliano: has anyone visited this town?

Pitigliano would fit your bill except for the fact that, in my opinion, it is too far from FCO for staying the night and, comfortably, making a morning flight. I'm remembering that the drive took us 3 hours. You should be at FCO 3 hours before your flight. You will need to check out of your lodging, drive, fill the tank (?), return your car, go to T5 for security check-in, and return to your departure terminal. Processing at FCO can be maddeningly slow. Can it be done? Of course, but I wouldn't recommend it. Depends on your tolerance for risk. All that being said, however, I also remember that the drive is very straight-forward, almost all superhighway and well-signposted.
Now, as to Pitigliano, it is quaint and interesting. It sits on a tufa cliff; and the historic center has pretty, narrow streets with well-maintained buildings. In the days before WWII, it had a large Jewish population. The synagogue and remains of other buildings can be visited. There is a remnant of a Renaissance aqueduct and a palazzo with local history artifacts, many Etruscan. A local wine, Bianco di Pitigliano, can be sampled at various spots around town.

We assume that your flight takes you outside the EU. For a flight within Europe, you could check in two hours ahead.

It's over 2 hr drive from Pitigliano to Fiumicino airport. Also consider that you should be at the airport at least 75-90 min prior for a EU flight and at a min. 2 to 2.5 hrs prior for a flight to North America. So to be sure that you are at the airport by 8:30 you would need to leave no later than 6am from Pitigliano. That would be too much stress and aggravation for me and I would not take a chance on the day of my flight

If you are looking for a quaint village outside Rome, the Colli Albani (Ariccia?) or Bracciano would be my choice.