The Institute was founded in 1869 as the commercial section of the Merchant Marine Institute (later known as the Nautical Institute). Starting in 1873 it began to purchase scientific instruments for educational purposes, and to publish the "Annals" of the Institute. In 1921, when the nautical institutes were put under the jurisdiction of the Ministry of the Navy, the Livorno Nautical Institute was separated from the Commercial Institute. On October 28, the new premises in Via Chiarini, still occupied by the school today, were inaugurated.

The educational collection includes laboratory instruments (projectors, telephone apparatus, an electromagnet, a Newton tube, a polarimeter, scales and nautical equipment) dating from the 1920s to the 1960s. The collection also includes 34 boxes of educational material, samples relevant to the processing of natural raw materials, dating from the 1950s.