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The church was begun in 1226–1265, on the hill of Camporegio which the Dominicans had received as a gift from the Malavolti family. It was enlarged in the 14th century resulting in the Gothic appearance it has now. However, aspects of the Gothic structure were subsequently destroyed by fires in 1443, 1456 and 1531, and further damage later resulted from military occupation (1548–1552).

The church is often called Basilica Cateriniana, due to the close proximity to which St. Catherine lived.

It is a large edifice built, like many contemporary edifices of the mendicant orders, in brick, with a lofty bell tower on the left (this was reduced in height after an earthquake in 1798). The interior is on the Egyptian cross plan with a huge nave covered by trusses and with a transept featuring high chapels. The entrance to the basilica is on the left side of the church because the area behind the façade is occupied by the raised structure of the Chapel of the Vaults.

The funeral of painter Simone Martini was held here in 1344. The church contains several relics of St. Catherine of Siena, who attended Mass here.

The old Chapter Room, the old Sacresty, the Refectory and the Dormitory were all built with the original Church and the Cloister was frescoed by Lippo Memmi and Lippo Vanni. Memmi did a small Maesta for the cloister. In 1372 Vanni painted an Annunciation for the cloisters.