During the 15th century, the municipality was under the control of the Church of Toledo, and was at that point in history called a villa.

The local copper mine, whose meager production supported the town's growth during the Renaissance, was abandoned during the mid-18th century.

The municipality is located on a granite mesa in the northernmost reaches of the Montes de Toledo.

It shares borders with the municipalities of Burguillos de Toledo, Nambroca, Chueca, Sonseca, Mazarambroz, and Layos.

60% of the territory of Ajofrín is cultivated, with 55% as vineyards, and the rest growing sugarbeets, olives, and cereal grains.