In 963 AD, the Holy Roman Emperor Otto the Great granted the castle and its court to the Canonina Aretino. In 1040, the Castle of Policiano was chosen as a wedding gift by Pietro Eriberto, heir of the historic Ghibelline family of Azzi, to future wife Gualdrada.
Only 4 years later, the castle became the property of Uguccione of the Marquises de Bourbon of Monte Santa Maria, one of the most important feudal families of the Middle Ages in Tuscany who were then appointed imperial vicars by Emperor Charlemagne.
During the 15th century, the castle became the property of the Capponi family of Florence whose 16th century coat of arms can still be admired today on the ancient walls
Leonardo da Vinci depicts the Policiano Castle in the “Codex Atlanticus” on the Map of the Val di Chiana. The Renaissance genius visited the castle during his trip in 1503 to discover the Arezzo area.
In 1848, the castle was purchased by the Chigi Saracini, a noble banking family of Sienese origin. In 1910 all the buildings owned by Chigi Saracini were taken over by Sidney Mary Hertz of Barbolani di Montauto who transformed the Castle into a farmhouse, renovating it with architectural style of that period, which is reflected in the front facade.
In the 13th century, the castle became a stopover for many travelers heading to Rome via the Via Francigena. It is thought that St. Francis of Assisi often resided in the castle during his travels from Assisi to the Franciscan sanctuary of La Verna.
In 1265, Guglielmo degli Ubertini, who went down in history as "the warrior bishop", took possession of the castle and obtained the oath of obedience and loyalty from 54 men. It was the warrior bishop who led the Ghibelline army against the Guelphs in the famous battle of Campaldino in which he perished.