Mentioned for the first time in a document dating from 1280, the hospital is undoubtedly of more ancient origin, but the date of its foundation is unknown since the archives were destroyed in a fire that broke out in 1444. Since the middle of the 16th century it has formed a single large building complex, enriched by donations bequeathed to it and by the legacies of the Rectors who succeeded one another in the Hospital Government. This process led to the development of a hospital proper, and the role of providing relief, which had distinguished it since the very beginning gave way to a strictly therapeutical orientation, with the presence of a physician and a surgeon.

Subsequent to poor management of the hospital’s assets, an attempt was made to control costs more efficiently. In 1782, a grand-ducal rescript limited its sphere of competence to that of treating patients, while with the reform of 1788 the hospital was definitively reorganised. From that time on, in fact, the Grand Duke himself chose the Rector, who no longer resided in the house annexed to the hospital, allocated instead to the Head Surgeon. After the Unification of Italy the hospital, like the others in Tuscany, passed under the administration of the State.

The collection of medical objects, consisting of surgical instruments, glassware and medical equipment dating from the 18th to the 20th century, is displayed in the Sacristy of the Church of San Francesco, adjacent to the hospital.