The existence of numerous Etruscan and Roman settlemens in this part of the country has been confirmed by the archeological finds consisting of necropoli and furnaces in the neighbourhood of Poggio all'Aglione, Bellafronte, Iano and Castelfalfi. There is also evidence pertaining to the Paleo-Christian period in the crypt of the Oratory of S. Biagio (500 metres far from Montaione). After the barbarian invasions new settlements were built around the old ruins, especially in the places that offered most safety, such as Paterno, Marrante, Sala and then the castle of Montaione, supplied as it was with numerous towers, and surrounded by solid walls. The area came under the jurisdiction of the Longobard Allone of Lucca, whose name must have been given to the castle itself since it was mentioned in ancient documents as "Mons Allonis", then corrected to become Montacone as it is written in a document dated 988. In 1118 the parish church dedicated to S. Regolo was built and remains a notable example of Romanesque architecture.

The town of Montaione was officially recognised in 1257, and then involded in the wars between San Gimignano, Volterra and S. Miniato, though it gravitated manly in Florence's orbit, submitting to the city's rule in 1369 and thence sharing its fate. It had its own set of statutes from 1370 on. From 1200 on the art of glass-making was carried out in Montaione. As late as the year 1700 an ordinance of the Grand Duke instructed Master Glassmakers at Montaione to teach their art only to their fellow townsmen. Following on the Empolese area and the Comunity became closed into an agricultural economy. At the end of the 19th century this comunity was deprived of a large part of its territory: Coiano, Meleto and Castelnuovo passed to Castelfiorentino; half of the territory left to Gambassi as a district was made into an independent township. Montaione remained within its walls until the last war, and then developed outside, especially from the '60' on.

The ancient town wall was damaged by German mines in 1944, and this resulted in the demolition of the two main gates, as well as numerous towers. The Palazzo Pretorio (14th century) where a number of old municipal stone and glazed terracotta coats of arms can be seen on the façade, stands out in the urbanistic planning of the town, based as it is on three parallel roads. The Palazzo today houses the Museum in which archeological finds from the surrounding territory are kept. The Church of S. Regolo, dedicated to S. Bartholomew in the 13th century, has a valuable painting (Madonna with Child of the 13th century) on a gold background attributed to a follower of Cimabue.