Montaione has no train station and no direct bus connection from Florence. The practical way to get here is by car — it is about 40 minutes southwest of Florence on the SP429 via Certaldo, or 30 minutes from San Gimignano via Gambassi Terme. The roads through the Valdelsa are quiet and scenic.
From Florence, a limited bus service runs via Certaldo and Gambassi Terme, but the schedule is infrequent and not practical for a day visit without a long wait. Certaldo, on the main Florence–Siena rail line, is the nearest train station — about 15 kilometres from Montaione — and a taxi can be arranged from there, though you will need to book in advance as there is no taxi rank.
A car is strongly recommended for exploring the area, as the main sights — San Vivaldo, Castelfalfi, and the surrounding countryside — are all several kilometres from the town centre on narrow country roads.