The church, overlooking the square of the same name, was built by the Franciscans in the mid-13th century on a pre-existing structure from the 12th century, initially dedicated to San Salvatore and later to San Leonardo. The building features a Romanesque-Gothic sandstone façade, with a slender mullioned window topped by a small rose window. On the lunette of the portal, one can admire a terracotta relief depicting Saint Francis instructing the doves on how to multiply, a work by local 20th-century ceramist Antonio Brogi.
The interior, in accordance with Franciscan tradition, consists of a single nave ending in a short transept with three vaulted chapels; the roof is gabled. Along the walls are 16th- and 17th-century altars, and one can admire works by Francesco Morandini, known as “il Poppi” (Crucifixion), Giorgio Vasari (Madonna with Saints Anna, Silvestro, and Antonio), and Salvi Castellucci (The Calling of Saint Matthew and The Annunciation to Saint Anne).
Notable is the third niche on the right, now empty, which once housed a Saint Francis by Margarito d’Arezzo; below it, protected by a grate, was the Holy Cross, a 13th-century reliquary of extraordinary value. Both works are now housed in the Pinacoteca. Also of great importance is the painted wooden crucifix imitating bronze by Giovanni Patriarca, and a wooden statue depicting Christ captured in the Garden of Gethsemane, sculpted by Sallustio Lambardi of Lucignano in 1651, which is carried in procession on Holy Tuesday by the Confraternity of Saint Anthony.
The choir loft, made of pietra serena (a type of sandstone) with a decoration of framed panels, dates back to 1546. The two central panels depict Saint Michael and Saint Francis, while the sides feature floral motifs. The entire structure is supported by two large brackets with double volutes and vegetal designs. To the left of the church lies a rectangular cloister, rebuilt in the early 17th century on a 13th-century portico, characterized by a double Tuscan-style loggia with a circular well at its center. Under the arches of the lower order, one can admire lunettes frescoed with scenes from the life of Saint Francis, a 17th-century work by Pelliccione da Colle.
Inside the cloister are the tombstones of many eminent Castiglionese figures who wished to be commemorated here. On the right side of the church, in 1560, the oratory of the Confraternity of Saint Joseph was built; in 1785 the confraternity was dissolved, and the oratory was sold to private owners.
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