The church was built in the Romanesque period (1000-1250). The first official record of the church dates back to the year of 1301 in the tax book of Fiesole. The church was partially burned down and abandoned due to the war between Florence and Siena in the year 1437. In 1445 the parish church was restored.
With a decree of Pope Julius II. from the 12. August 1508, the church San Piero was allocated to the monastery of San Leolino in Panzano. To this day the most important artworks of San Piero can be viewed in the monestary church of San Leolino. Namely the triptych depicting the wedding of Saint Katharina in the presence Saint Peter – Sienese school; 2nd half of the 14th century and a painting by Meliore di Jacopo, depicting the Madonna on the throne with child flanked by Saint Peter and Saint Paul dated 1270.
1737 San Piero functioned as the home of the monasteries prior and a small monastic community.
The bell tower and church roof collapsed and are no longer in place today. In 2004 the church was put under monumental protection as an important heritage site in the region of Siena.