The name Montelifré probably derives from Lombard etymological origins, possibly Liutfrido or Lifredi.
The first written documentation of the castle’s presence dates to before the year 1000 A.D. The first definitive documentation of the entire town, from the year 1213, states: “The heads of sixteen families of the land declared their allegiance to the Republic of Siena.”
The Cacciaconti of Scialenga, Imperiali vassals and the lords of Montisi and Asciano were in power until 1328, when the Consorteria of the Tolomei took control. In 1348 it was acquired by the Martinozzi family, originally from Montepulciano, a patrician Sienese family belonging to the Monte dei Nove government.
The Monti in Siena were a type of oligarchic political-economic consortium in which membership was inherited through birthright. The Monte dei Nove was comprised of, among others, the Tolomei, Malavolti, Saracini, Piccolomini and Salimbeni families, to whom the Martinozzi owed their allegiance.
In the second decade of the 1500s the Martinozzi allied with Florence and Montepulciano to overthrow the Republic of Siena, hosting and stationing three hundred soldiers armed with cannons in their castle at Montelifrè.
The government of Siena ordered Montelifrè besieged in April of 1527 but thanks to the material support of Florentine and Papal forces in favor of the Martinozzi, the siege was unsuccessful.
After the sack of Rome, several months later on account of the lack of protection from Florence and Montepulciano, Siena returned to siege on Montelifrè, this time seizing and destroying it, creating the ruins still seen today.
The town was slowly rebuilt over the 1600s and 1700s, always under the control of Montepulciano.
The church of San Biagio was placed under the spiritual auspices of the Cura delle Sante Flora and Lucilla di Montisi, where there was also a small ceramics industry and a manufacturer of silk.
The town is currently inhabited by the descendents of the Martinozzi families who reside there year-round, with parts of the area having been developed as tourist sites.