North east of Capalbio is the extraordinary little town of Pitigliano, one of three along with nearby Sovana and Sorano perched on steep volcanic ridges of tuft rock and linked by a network of pathways and roads cut into deep trenches called Cave del Vie. Pitigliano has ancient Bronze age and Etruscan origins, with ruins of a necropolis, ancient city walls, temples, and many ancient artifacts on display in the local museum.

In the early middle ages it belonged to the Aldobrandeschi family, but passed to the Orsini in 1293 as a wedding dowry. The Orsini battled regularly with Siena, and eventually ceded the town to the Medici in 1604 to settle a family debt. From the 16th century onwards this extraordinary little town supported and protected a large Jewish population, gave refuge to Sephardic exiles from Spain, and saved them from racial discrimination and persecution during the second world war. The synagogue in the heart of the Jewish quarter in the old town is only one of the numerous beautiful buildings, churches, villas, and castles nestled within its walls.