How often do buses run between Florence and Siena on Sundays?
Italy - Florence to Siena
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A perfect day in Firenze

Timetable in
http://www.sitabus.it/sita-toscana/Firenze%20-%20Siena.pdf
Express non-stop service (75 min): 4 times
Direct via Poggibonsi (95 min+): 9 times
Thank you so much Alec for the information - now I have another question. If I take the Express Service on a Sunday at 14:10 and plan to arrive in Siena at 13:25, where is the bus stop in Florence?
At the bus station across the street from Firenze Santa Maria Novella train station shown in the center of the PDF supplied above.
AUTOSTAZIONE SITA
Via S. Caterina da Siena, 17 R
(Stazione F.S. S.M.N.)
By the way, there are a few other stops in Florence that may be more convenient listed below the bus station, but these will be stops on a street, not an actual station. I'm not sure if you can purchase tickets on the bus, so the station may be the best bet for you.