The Livorno province is a long coastal strip in the center of the region. It includes most of the Tuscan archipelago and Elba, 20 km from the coast, the third largest Italian island after Sicily and Sardinia, with 8 "comuni": Portoferraio, Campo nell'Elba, Capoliveri Marciana, Marciana Marina, Porto Azzurro, Rio Marina and Rio nell'Elba.

The province derives from the homonymous district of the Grand Duchy of Tuscany, which included however only the city of Livorno and the islands of Elba, Gorgona, Montecristo and Pianosa.

In 1925 Costanzo Ciano promoted the expansion of the province with the island of Capraia from the Province of Genoa and Bibbona, Campiglia Marittima, Castagneto Carducci, Cecina, Collesalvetti, Piombino, Rosignano Marittimo, Sassetta and Suvereto from the province of Pisa.