 Scarlino appeared before the year 1000 as a possession of the Aldobrandeschi family, and was later handed over to the bishops of Roselle and then the Alberti family.In the 13th century it was acquired again by the Aldobrandeschi, but later it passed to Pisa and then the Appiani of Piombino.Scarlino remained part of the Principality of Piombino until the early 19th century, when it became part of the Grand Duchy of Tuscany.