The establishment of the village of Catignano dates back to around the year 1000. Without doubt, the history of the village is inextricably linked with that of a powerful family of Lombard origin, who assumed the name Cadolingi, after the head of their dynasty, Cadolo.
In this period, the Cadolingi exerted their authority over large tracts of territory on the left bank of the River Arno, from the Settimo plain through Lastra and Fucecchio all the way to the flatlands around Lucca. Of pre-eminent importance for the family was the retention of control over what was, at the time, one of the principal thoroughfares in the region, the via Francigena.
A great number of castles were built along this arterial highway, particularly at and around the strategic points where the via Francigena intersected with other important roads such as the via Volterrana. In the district of Gambassi alone, there were a total of six castles, most of them built at the behest of the Cadolingi and located on the via Francigena running from south-east to north-west.
One of these was Catignano Castle, an edifice noted in documents written as early as 1075. In 1115, along with several other fortifications in the Val d'Elsa area, the castle came under the control of the church in Volterra, and yet during the course of the 14th century, even at time when it was part of the sphere of influence of San Gimignano, it maintained a higher level of autonomy than most other castles.
It is worth remembering that, in 1294, the castle had become part of the contado of Florence.

Nowadays, substantial sections of the formwork of the castle remain relatively intact, with two truncated brick towers still standing. Along the same road, a large number of religious buildings are also still visible.
These include the church of Santo Stefano in Gambassi, the parish of Santa Maria in Chianni (visited and described by Sigeric, Archbishop of Canterbury, on his journey home from a pilgrimage to Rome), the church of San Salvatore in Fogneto, the rectory of San Giovanni in Varna and the church of San Martino in Catignano, where the Cadolingi family worshipped.
This church is mentioned for the first time in the tithes of 1275-76, and also in later works such as the Ecclesia S. Martini de Catignano.
It achieved some considerable level of importance and was charged with the responsibility of supervising a number of other churches, including the church of Santa Lucia, as well as two hospitals.

Over the centuries, the church may perhaps have been subject to other modifications (even if no trace of the medieval architecture is visible today due to the plaster which was applied over it at some time in the past), but we do know for certain that in the early years of the 20th century it underwent substantial reconstruction (the new facade and bell-tower were inaugurated in 1910), while retaining a portion of the perimeter wall of the original structure.
The orientation of the church was certainly altered, but given that the facade of the church now faces north, it is probable that the building was rotated on its axis by no more than 90.
In addition, the via Francigena also played host in medieval times to at least two different hospitals, the hospedale pauperum et transeuntium egenorum in Catignano and the hospedale pauperum in Gambassi.
The hospital in Catignano was founded within the eponymous castle in 1280 by the cumfraternitas et societas beate virginis Marie de Catignano for a purpose described at the time as hospitalitatem et substentationem pauperum ettranseuntium egenorum. Along the road that leads to Varna, the place name 'Annunziatina' indicates the ancient site of the hospital.