The Naval Academy stands on the former site of the Hospital of St. James, built in the 1640s for the quarantine of ships' crews from the Levant, which were previously diverted to the islands of Giglio and Elba.

Dux navigationis et hominibus salutis publicae Vindex mercibusque graviora pestilentiae suspicion notatis tutius expurgandis remotiorem hanc er Insulam porticus designavit construxit ann.

One consisted of the palace housing the officers, which still exists today, with a semicircular facade facing the entrance to the dock.

At the center of the dock entrance, isolated in the water, sat the tower of San Rocco (destroyed during World War II), which was connected by a wooden walkway.

During World War II, because of the bombings that struck Livorno in July 1943, the Accademia Navale was forced to move to Venice and then, after only two months, to Brindisi, where it remained until 1946.

Since the bombing had heavily damaged many of the buildings of the city and the structures that housed the academy, it was necessary at the end of the conflict to start substantial reconstruction efforts and infrastructure improvements, which took over twenty years and included, in 1966, the addition of "Palazzo Studi", which now houses the science labs and other specialized classrooms.

The Accademia Navale complex covers approximately 2,300,000 square metres (25,000,000 sq ft) and includes, classrooms, laboratories, dormitories, a swimming pool, a gym, libraries, cinemas, and auditoriums.