Volterra has no train station. The nearest rail connection is Saline di Volterra on the Cecina–Volterra branch line, served by infrequent trains from Cecina on the coastal Pisa–Grosseto line; a bus connects the station to Volterra (7 km). Practically speaking, arriving by car is far easier.
By car from Florence, allow about 90 minutes (90 km via the Superstrada del Palio toward Siena, then secondary roads through Colle di Val d'Elsa). From Siena the drive is about 50 km and takes around an hour. From Pisa, allow an hour via Pontedera.
CPT buses run from Volterra to Pontedera (with connections to Pisa), Siena, and Florence. The journey to Florence takes around two hours. The bus station is just outside Porta Fiorentina, the main northern gate.