Former member of the Italian Communist Party, he joined the Democratic Party of the Left and was elected Mayor of Grosseto in substitution of Flavio Tattarini on 23 January 1992, after the election of mayor Tattarini at the Italian Parliament.

[1][3] He ran for a new term at the 1997 Italian local elections, but was defeated by the centre-right candidate Alessandro Antichi.

[2] Valentini was also president of Fondazione Grosseto Cultura (2012–16)[4] and director of the historical institute ISGREC (2019–21).

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