The territory around Massa Marittima was inhabited since prehistoric and proto-historical times, as evidenced by numerous finds dating from the Paleolithic to the Bronze Age.

In 1554, during the war between the Republic of Siena and Duke Cosimo de' Medici, the Massa fortress capitulated, besieged by the Spaniards led by Carlo Gonzaga.

During the Medici rule, the city experienced an initial attempt of recovery by Grand Duke Ferdinando I, but none of its successors showed interest in the fate of Massa and Maremma: the only interventions were related to Valpiana's ironworks.

Giuseppe Garibaldi himself went to Massa Marittima, and later became an honorary citizen; some young Massetans helped him to reach Cala Martina to embark at Porto Venere in September 1849.

During World War II, Massa was a centre of partisan activities, and several of its citizens were killed by German and Italian troops in retaliation.

Today, the city mainly lives in tourism, thanks to the presence of numerous works of art and the valorization of ancient crafts, mainly linked to its minerary past.