It was founded in 1834 by Grand Duke Leopold II of Tuscany for the workers of a new ironworks plant.

However, the area was already settled in Etruscan and Roman times, and a medieval castle (Castello di Valli), whose ruins overlook now the modern town from a nearby hill, existed since at least 884.

The city has been awarded the Bandiera Blu ("Blue Flag") every year from 2000 to 2007 for the cleanliness of its beaches and seawater.

USD Follonica Gavorrano born of the merger between the teams of Gavorrano and Follonica, militant in Serie D. The Via Aurelia highway (SS 1), which runs from Rome to the Franco-Italian border, passes close by the city.

The railway linking Reggio Calabria in the south and Turin in the north runs through the city, providing direct railway connections to the cities of Grosseto, Rome, Turin, Naples, Pisa and La Spezia, among others.