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Mayordomo mayor to the Spanish kings

In 1541 Fernando Álvarez de Toledo was named Mayordomo Mayor del Rey de España (High Steward to the King of Spain) by Charles I of Spain. Alba kept this office in court until the death of the monarch in 1556.

In 1546, Charles I invested the Duke of Alba Grand Master as knight of the Illustrious Order of the Golden Fleece.

From 1548 King Charles intensified the preparations of Prince Philip as his successor in the Spanish Monarchy, and he named Duke of Alba mayordomo mayor of his son to prepare Philip for his new role. Fernando took Philip on a tour around Europe that lasted until 1551. Fernando accompanied Philip to England to attend his marriage to Mary Tudor. The Duke was one of fifteen grandees of Spain who attended the ceremony in the abbey of Winchester on 25 July 1554.

After the death of Charles, the new King Philip II maintained Alba as mayordomo mayor until the death of the Duke in 1582.

In 1563, King Philip II created the title Duke of Huéscar to be bestowed on the heir of the Dukes of Alba. Fadrique Álvarez de Toledo, son of Fernando became 1st Duke of Huéscar.

In 1566, Alba's son and heir, Fadrique, broke his promise of marriage to Magdalena de Guzman, lady of Queen Anne of Austria, which led to his arrest and imprisonment in the Castle of La Mota in Valladolid. The following year he was released so he could go to Flanders with his father to serve in the military. In 1578 Philip II ordered the case against Fadrique reopened. It was discovered that in order to avoid marriage, Fadrique had secretly married María de Toledo, daughter of García Álvarez de Toledo and Osorio, IV Marquess of Villafranca del Bierzo, using a permit issued for that purpose by his father the Duke of Alba. Fadrique was sent to prison, in the Castle of La Mota. Fernando, Duke of Alba was banished from the court for one year for "breaking the strict court protocol." The Duke went into exile in Uceda, where his secretaries Fernando de Albornoz and Esteban Ibarra likewise spent their punishment.