From the Piazza del Campanile, passing through the Pieve di San Lorenzo, and the arch of the Canonica, you reach the Church of San Giorgio, another important symbol of the village of Montemerano.

The Church is a true example of Sienese art from the mid-15th century, the building was born as a church outside the city in 1300, was rebuilt in the first decades of the 1400s and consecrated on 30 October 1430 at the hands of the Bishop of Sovana, Antonio del Wedding ring.

The structure of the church is very simple, but impressive and the interior houses real masterpieces of art:

• a polyptych with the Madonna and Child enthroned and the Saints, attributed to Sano di Pietro and painted on commission in 1458. Its location, the integrity of the panel and the frame (made in late Gothic style), and the presence, in addition to Saints Peter and Francis, also of Saint George and Saint Lawrence, patron saints of the town, testify to how the painting was commissioned specifically for this church.
• a polychrome statue of Saint Peter, life-size and made of wood, was created around 1450 and attributed to Lorenzo di Pietro, better known as Il Vecchietta
• the left transept houses a panel depicting the Assumption, also dating back to 1450 and created by Pellegrino di Mariano Rossini
• the altar of the right transept houses a sixteenth-century fresco depicting the Madonna della Rondine, also from the Sienese school
• a processional cross of Renaissance origin made of gold foil, with a carved wooden tabernacle
• the small temple, in Renaissance style, surmounted by a dome, has six faces, five panels are painted depicting the saints San Giorgio, San Lorenzo, the Virgin Mary and two Angels, while one features golden lozenges
• the most famous and important work of the Church, however, is the Madonna della Gattaiola, a tempera on panel over 2 meters high. The peculiarity of this work is the presence, at the bottom right, of a circular hole which, according to tradition, would have been made by the parish priest to allow the passage of a cat, the table in the past was in fact also used as a door to the rectory
• Finally, the cycle of frescoes dedicated to San Giorgio, very interesting because in one of the frescoes which depicts the holy knight dragging the dragon inside the walls, architectural elements can be recognized which lead back to Montemerano itself and the church square.