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Castaños was one of the most important military officers during the Peninsular War, reaching the position of Chair of the Regency Council of Spain and the Indies ("de facto" head of state) in 1810. In 1833, Queen Regent Maria Christina of the Two Sicilies, in the name of her daughter, Queen Isabella II, granted him with the title of Duke of Bailén, to honour his actions in the Peninsular War and, specially, in the Battle of Bailén, where the Napoleonic army was defeated at open field for the first time, which also caused the flight of Spain from King Joseph Bonaparte.