Be ready for morning pickup at your hotel in Livorno, then climb into your private vehicle and set off for the area around Siena. The type of vehicle will depend on the number of people in your group.
Relax on the journey to San Gimignano, located roughly halfway between Siena and Florence. Once you arrive, you're on your own to design your own tour of the famous medieval architecture of this walled town, taking in the feudal atmosphere that hints at the town's history. San Gimignano is famous for its white wine, called Vernaccia di San Gimignano, and its export of saffron.
Back in your private vehicle, continue to Volterra, recently famous as a filming location for the 'Twilight' series of films. Visit the 800-year-old city hall and learn about the history of the alabaster export business. On Via Porta all'Arco, or 'Artisan Lane,' you'll find book binderies and paperies, jewelry stores, and leather and bronze shops, among others.
When you've finished up in Volterra, watch the scenery on your return trip to Livorno for drop-off at your hotel.