He was born the second son of José Álvarez de Toledo y Silva, 18th Duke of Medina Sidonia, and Rosalía Caro y Álvarez de Toledo, daughter of the 4th Marquis of La Romana.
He was originally the Marquis of Molina, but on the death of his older brother Alonso, he became the heir to all the titles of the house of Medina Sidonia.
He managed his estate very well, but when he inherited the bulk of the family assets, he had to deal with a huge amount of debt that his father had acquired.
The most urgent ones were solved with the sale of the Coto de Doñana to Guillermo Garvey, for 750,000 pesetas.
As Grandee of Spain, he held important positions at court, such as Gentleman of the King's Chamber, or Chief Knight of María de las Mercedes, Princess of Asturias.