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Francisco de Paula was born at Toulouse, France third child of Infante Enrique, Duke of Seville (1823–1870), (son of Infante Francisco de Paula of Spain and Princess Luisa Carlotta of Naples and Sicily) and his wife, Elena María de Castellví y Shelly (1821–1863), (daughter of Antonio de Padua de Castellví y Fernández de Córdoba, Count of Castellá and Margarita Shelly) his mother was of Valencian and Irish ancestry.
She was born at the royal Palace of Madrid on 12 October 1834 as the eleventh child and sixth daughter of Infante Francisco de Paula of Spain, younger brother of King Fernando VII of Spain, and his wife, Princess Luisa Carlota of Bourbon-Two Sicilies.