In 1216, a small chapel was dedicated to St Lawrence by the bishop of Zamora, Martin Arias, originally from Santiago. The foundational document, granted by King Alfonso IX of Leon, still exists in the archive of Santiago Cathedral. Legend has it that Pedro Muñiz withdrew to the seclusion of this chapel after being falsely accused of necromancy.

Later on, in the 15th century, it came under the ownership of the Counts of Altamira who granted usufruct of the monastery to the Franciscan Order which occupied it until confiscation by the State in the 19th century. The Duchess of Medina de las Torres, the great-grandmother of the current owner and the daughter and heiress to the Count of Altamira, sued the State to recover ownership. Since the monastery had never actually been the property of the monks, the court found in her favour, and the property was subsequently restored.

The Emperor Charles V retreated to the monastery during Holy Week in 1520. Remains of the early Romanesque construction can be seen in the lower part of the church. The high altar and the praying statues of the Marquises of Ayamonte, Francisco de Zúñiga and Leonor Manrique, were originally located in Seville in the Church of St Francisco, which also belonged to the same family. When it was demolished, the founders’ descendants preserved the statues and, in 1882, the Duchess of Medina de las Torres had them installed in this monastery which, once again, was in the possession of her family. They were carved in Italy in the early 16th century out of Carrara marble by the brothers Aprile and Pier Angelo de la Scala, as a commission from the Marquise of Ayamonte to honour the memory of her husband who had died very young. The image of the Virgin and Child in a side altar is the work of the Sevillian sculptor Martinez Montañés (17th century). The cloister dates from the 17th century, as does the box hedge. The fountain bears a 15th century image of the Virgin. The gardens retain their conventual layout. The Galician poetess Rosalía de Castro spent many hours in the oak woods and from them took inspiration for her poems.