Probably designed by Lorenzo Nottolini, the Hospital was begun around 1825 thanks to Count Niccolò Demidoff's contributions to the Lucca Hospital, which operated the Baths. The Hospital remained open from June 15 to September 15, providing full healthcare service to those who could not afford the cost of thermal treatments. Pharmaceutical service was provided by the pharmacy of the Baths.

In 1836 the flooding of the little stream Camaione destroyed the wooden bridge that joined the building to the elegant neoclassical chapel designed by Giacomo Marracci. Prince Anatolio Demidoff, Niccolò’s son, had a new bridge built of bricks and marble, with a light arcade, to the project of Giuseppe Pardini; it is still visible today. The sides of the bridge are decorated with marble bas-reliefs representing the coat-of-arms of the Demidoff family and symbolic images of medicine.

The entire complex of the former Demidoff Hospital (now Villa Demidoff) is occupied today by an alternative medicine centre (Global Village Association – Holistic Medicine Centre for Psychological and Physical Well-being).