Murlo borders the following municipalities: Buonconvento, Civitella Paganico, Montalcino, Monteroni d'Arbia, Monticiano, Sovicille.

From 1189 to 1778 it was the seat of the homonym "Feudo vescovile di Murlo", ecclesiastical signoria governed by the bishop of Siena, of which remains the palace and the adjacent church of San Fortunato, where the Bishop celebrated religious rites.

[4] The hill of Poggio Civitate was an ancient settlement located in the commune and currently the site of archaeological investigations.

The territory, exclusively hilly, is between the valley of the river Merse and the Val d'Arbia.

Other minor localities of the territory are Aiello, Belcano, Campeccioli, Campolungo, Campriano, Casanova, Crevole, Cucculeggia, Filetta, Fontazzi, Formignano, Frontignano, Gonfienti, Lupompesi, Macereto, Miniere di Murlo, Mocale, Montepertuso, Montorgiali, Olivello, Pacanino, Palazzaccio, Piantasala, Pieve a Carli, Poggiobrucoli, Poggiolodoli, Pompana, Resi, San Giusto, Santo Stefano, Tinoni, Vallerano.