The earliest news about Montelpio date back to 1356, in an act of the synod of Volterra  in which reference is made to a church with a refuge, also known as a “mansion”, used by the Knights Templar.

In the small village was the parish church of San Martino at the time, an important parish church, which was demolished later in modern times by order of a marquis of the area who, according to the legend, was run over by his horse as a divine punishment for having it demolished. The Chapel of San Domenico was later built in its place.

The village was home to important noble families including the Frescobaldi, the Gaetani and the Quaratesi who appreciated not only the small village but also its surroundings, rich in woods, vineyards and olive trees.

Some historic buildings are still visible today:

• Villa Mazzetti, located in via San Martino, built in the 19^th century on a facility dating back to 1248. You can still see the coat of arms of the Gaetani on it.
• Villa Ballati Neri, a manor house, originally from the period between the 13th and 14th centuries.