It seems there was a farmhouse which gave rise to a settlement reached sufficient entity that once reconquered, was in the family properties of Munio Alfonso.
The first written references are on Ajofrin are late due to low population and urban entity, both Muslim and Christian era. In 1267, Ajofrín is cited as the Sista farmhouse, located in a crossroad.
Ajofrín would be an example of reforestation carried out by the nobility, since it is aware of a will of Munio Alfonso, dated in 1139, where it is stated that his father, Adefonsus Munio, received Ajofrin donated by Alfonso VI, perhaps as reward for the services we could provide. Munio Alfonso left Ajofrín their children (Alfonso and Matthew) and from then until 1266 has not written news of this municipality.
In 1267 Alfonso Mateos, along with his brother Fernando, agree to build a single fund with two-thirds between both possess in the farmhouse of Ajofrín, in order to avoid the disintegration of the assets to the passage of the succession of heirs. Creating therefore a birthright, staying as Fernando and later became owner several heirs succeeding several conflicts tenure.
The secular lordship of Ajofrín becomes ecclesiastical in 1384, because Ines Barroso Garcia, owner of the village of Ajofrín, decides to donate, reserving the usufruct during his lifetime, to the dean and chapter of the church of Santa María de Toledo.