The territory of the present Municipality of Montespertoli played an important role in past times, surely since the Etruscan period, because of its road network which enabled Florence to trade towards Volterra and Siena along the Via Volterrana. This road actually crossed the territory of Montespertoli from North to south and joined the Via Francigena at Certaldo. Scattered along the Via Volterrana can be found settlements of the nobility dating back to the early Middle Ages: to the North near Montegufoni there was the castle of the Ormanni which was destroyed by the Florentines in 1135. After the destruction of tha Ormanni castle, Gugliarello Acciaioli from Brescia bought a lot of land in the area and one hundred and fifty years later, on 12 September 1310, the Great Seneschal Niccolò Acciaioli was born there. The Acciaioli bequeath the church of San Lorenzo in Montegufoni works of art of very fine quality: a Crucifix by Taddeo Gaddi. The Acciaioli family decayed early in the XVIIth century and all their estates were bought by the Usibardi family, extinct in 1663. Then a descendant of another branch of the Acciaioli line, Donato, succeeded in buying back all the family properties and starting a new period of wealth which lasted throughout the XVIII century.
The castle standing to one side of Montespertoli, today the property of the Sonnino, originally belonged to the Signori of Montespertoli, a branch of the Dukes Alberti from Mangona but, since ttheir family became extinct in 1393, they bequeathed all their properties to the Machiavelli. The estates of this family stretched over almost two thirds of the present Municipality of Montespertoli and we owe them the very great number of art in most churches of the territory. Montespertoli, of medieval origin, had its first church inside the castle of the Signori of the town, and only at the beginning of the XVth century the Churh of Sant’Andrea, presently in Piazza Machiavelli, was built and later restored after the damages caused by the Second World War. In the territory of Montespertoli the Parish-church of San Piero in Mercato represents together with the village of Lucardo the most ancient centre dating back to the early Middle Ages. Today the oldest traces left of the church date from the Romanesque period, but we can reasonably assume that a building of a very simple structure stood on the same spot before the year one thousand and was destroyed in the course of the building activity of the XIth century. During the XIVth century San Piero in Mercato was the seat of the Podestà and of the League of three parishes: San Piero in Mercato, San Pancrazio and Coeli Aula. At the end of the XVth century the important market held in San Piero and the seat of the Podestà were moved to Montespertoli. The small Sanctuary of St. Mary of Peace, in the Convent of Botinaccio, built in the XVI century, has been expanded from year to year to get the present dimension. It became Franciscan Friars’ property until the French invasion in the decade of the last century. In the chapel, there are some frescoes dating back to around 1600.