Montegufoni stands on the ancient Via Volterrana, the road taken by Charlemagne and other emperors to reach Florence or Rome and which passes through Volterra and Siena.

[2] In 1386, Donato Acciaioli, a man who held the titles of Duke of Athens, Senator of Rome and Gonfaloniere of the Republic of Florence, built the tower that still dominates the castle today.

Around 1650 Donato, with his wife Anna Maria Altoviti, restored the entire castle, giving it the appearance it still has today, connecting the seven buildings that until then had been separate.

[6] During World War II, to avoid them being stolen or damaged, 261 works of art, including the Adoration of the Magi by Domenico Ghirlandaio, the Primavera by Sandro Botticelli and the Ognissanti Madonna by Giotto were hidden in Montegufoni, as in many other places scattered throughout the Tuscan countryside, thanks to the work of people such as Giovanni Poggi, an official of the Fine Arts and director of the Uffizi, and Cesare Fasola, but also of ordinary citizens.

In 1966, Sir Osbert, who had become a famous British author, settled permanently at the castle, often living there with his partner, the novelist David Stuart Horner.

[10] The Castle's Church of San Lorenzo contains a fresco by Giovanni Domenico Ferretti, a Rococo painter of the Florentine school; a painted crucifix by Taddeo Gaddi; the Madonna and Child (Italian: Madonna col Bambino) from the workshop of Lippo di Benivieni, dating from the Trecento, is now preserved at the Museo di Arte Sacra in Montespertoli.