Trenitalia operates a train from Livorno to Siena hourly. Tickets cost $5 - $13 and the journey takes 51 min. Trenitalia also services this route hourly.
How to get from Livorno to Siena
From Livorno C.Le train to Empoli then train to Siena. 2 h 23 min 16€. From Livorno P.Za Della Repubblica line 010 bus to Battisti, bus to Pisa, then night bus to Siena. 4 h 11 min 20€. From Livorno drive to Siena. 1 h 44 min 18€.