The current station was built to an Art Deco design and was completed in 1935, replacing another station at Madonnina Rossa. It serves as the midpoint and terminating station of most trains on the Central Tuscan Railway, with current services mostly running either to Chiusi-Chianciano Terme or Empoli, a large percentage continuing to Florence SMN. The section from Siena to Empoli opened in 1849, but the sections south of Siena opened gradually: the Siena-Sinalunga section was completed in 1859, and the last section was completed over the next 3 years, meaning the line was fully completed on 24 July 1862. The line to Grosseto has had two different routes. In 1872 a line was opened from Asciano to Grosseto via Monte Antico, with trains using the Central Tuscan line from Siena before diverging at Asciano onto the new section. In 1906, a faster line was proposed, running down to Buonconvento before travelling alongside the Ombrone river to Monte Antico. This was opened in 1927. This station was opened in 1935, and has 6 platforms in operation. Platforms 1-5 are through platforms, and there is a bay platform to the north alongside platform 1, identified as platform 1 tronco. There are various sidings around the station, notably alongside the bay, where rolling stock for the historic steam and diesel Trenonatura services along the Asciano-Monte Antico line is sometimes kept.
The station is currently managed by Rete Ferroviaria Italiana (RFI). However, the commercial area of the passenger building is managed by Centostazioni. Train services to and from the station are operated by Trenitalia. Each of these companies is a subsidiary of Ferrovie dello Stato (FS), Italy's state-owned rail company.
A series of escalators connects the train station with the old city on top of the hill.