The town was a Neolithic settlement and an important Etruscan center (Velathri or Felathri in Etruscan, Velàthre, Βελάθρη in Greek) with an original civilization. The site is believed to have been continuously inhabited as a city since at least the end of the 8th century BC. It became a municipium in the Roman Age. The city was a bishop's residence in the 5th century, and its episcopal power was affirmed during the 12th century.
With the decline of the episcopate, Volterra became a place of interest of the Florentines, whose forces conquered Volterra. Florentine rule was not always popular, and opposition occasionally broke into rebellion. These rebellions were put down by Florence.
When the Florentine Republic fell in 1530, Volterra came under the control of the Medici family and later followed the history of the Grand Duchy of Tuscany.
Pinacoteca (Art Gallery) in Palazzo Minucci-Solaini. The Gallery was founded in 1905 and consists mostly of works by Tuscan artists from 14th to 17th centuries. Includes a Deposition by Rosso Fiorentino.
Guarnacci Etruscan Museum, with thousands of funeral urns dating back to the Hellenistic and Archaic periods. Main attractions are the bronze statuette "Shadow of the Night" and the sculpted effigy of an Etruscan couple in terra cotta.
The Etruscan walls, including the well-preserved Porta dell'Arco (3rd-2nd centuries BC) and Porta Diana gates.
Linda Proud's A Tabernacle for the Sun (2005), the first volume of The Botticelli Trilogy, begins with the sack of Volterra in 1472. Volterra is the ancestral home of the Maffei family and the events of 1472 lead directly to the Pazzi Conspiracy of 1478. The protagonist of the novel is Tommaso de' Maffei, half brother of one of the conspirators.
Volterra is the site of Stendhal's famously disastrous encounter in 1819 with his beloved Countess Mathilde Dembowska: she recognised him there, despite his disguise of new clothes and green glasses, and was furious. This is the central incident in his book On Love.
Volterra is mentioned repeatedly in British author Dudley Pope's Captain Nicholas Ramage historical nautical series. Gianna, the Marchesa of Volterra and the fictional ruler of the area, features in the first twelve books of the eighteen-book series. The books chart the progress and career of Ramage during the Napoleonic wars of the late eighteenth and early nineteenth century, providing readers with well-scripted articulate details of life aboard sailing vessels and conditions at sea of that time.
Volterra also where Valerio Massimo Manfredi's The Ancient Curse is set, when a statue called 'The Shade of Twilight' is stolen from the Volterra museum.
Volterra is featured in Jhumpa Lahiri's 2008 collection of short stories, Unaccustomed Earth. It is where Hema and Kaushik, the protagonists of the final short story "Going Ashore," travel before they part.