The hill that Capalbio stands on, surrounded by the woods of the nature reserve and olive groves, was once bare white alabaster rock which glittered in the sunlight and from which it is though the latin name for Capalbio – Campus album – comes from. The hill was inhabited during the iron age, and was an Etruscan settlement in the eighth and seventh centuries BC before the Romans took it.

After the fall of the Roman Empire in 476 AD it was invaded by Ostrogoths and Lombard barbarians, and first mentioned in historical records in 805, when Charlemagne, the Holy Roman Emperor, donated it to the Abbey of the Tre Fontane in Rome, before being sold to the powerful Aldobrandeschi nobles in the 11th century, who fortified it and then spent centuries battling the forces of Orvieto and Siena, pillaging by Saracen pirates along the coast, and the ravages of malaria.