|Oscar I, King of Sweden||1799||1859|| |- |Francis, Duke of Calabria||1836||1894||later King Francis II of the Two Sicilies |- |1845||Henri, Duke of Aumale||1822||1897|| |- |rowspan=5|1846||Eugène Lamoral, Prince of Ligne||1804||1880|| |- |Agustín Fernando Muñoz, Duke of Riánsares||1808||1873|| |- |Antoine, Duke of Montpensier||1824||1890||youngest son of the King Louis Philippe of the French; husband of the Infanta Luisa, sister of Queen Isabella II of Spain |- |François, Prince of Joinville||1818||1900|| |- |Pedro, Crown Prince of Portugal||1837||1861||later King Pedro V of Portugal |- |rowspan=2|1847||Ramón María Narváez y Campos, 1st Duke of Valencia||1800||1868|| |- |José María Osorio de Mosco de Carvajal, 17th Duke of Sessa, 19th Duke of Trastamara and 14th Count of Altamira||1828||1881|| |- |1848||Frederick VII, King of Denmark||1808||1863|| |- |1849||Juan Roca de Togores, 3rd Count of Pinohermoso||1801||1883|| |- |1850||Louis Napoleon Bonaparte, President of the French Republic||1808||1873||later Napoleon III, Emperor of the French. Co-Prince of Andorra. |- |rowspan=2|1851||Francisco Martinez de la Rosa||1787||1862|| |- |Joaquín Fernández de Córdoba, 6th Duke of Arion||1787||1871|| |- |rowspan=6|1852||Francisco Javier de Istúriz||1790||1871|| |- |Nicolás de Osorio y Zayas, 16th Marquis of Alcañices, 15th Duke of Albuquerque and 15th Duke of Ledesma||1793||1866|| |- |Juan Bravo Murillo||1803||1873|| |- |Albert Edward, Prince of Wales||1841||1910||later King Edward VII of the United Kingdom, Emperor of India |- |Louis, Count of Trani||1838||1886|| |- |Charles Louis, Count of Ficquelmont and of the Holy Roman Empire||1777||1857||heir from a prominent noble family from Lorraine, former imperial ambassador and former Minister-President of the Austrian Empire |- |1853||William, Prince of Prussia||1797||1888||later King William I of Prussia and German Emperor |- |1854||Robert, Duke of Parma||1848||1907|| |- |1855||Charles, Crown Prince of Sweden||1826||1872||later King Charles XV of Sweden |- |rowspan=3|1856||Juan Carlos Francisco, Duke of Saldaña||1791||1876|| |- |Napoleon, Prince Imperial||1856||1879||son of Emperor Napoleon III of France |- |Prince Adalbert of Bavaria||1828||1875||son of King Louis I of Bavaria |- |rowspan=3|1857||Nicholas, Tsarevich and Grand Duke of Russia||1843||1865|| |- |Alexander, Prince Gorchakov||1798||1883||Foreign Minister of Russia |- |Alfonso, Prince of the Asturias||1857||1885||later King Alfonso XII of Spain. Head of the Order from 1870/1874 |- |rowspan=2|1859||Infante Ferdinand of Spain||1859||1872||nephew of Queen Isabella II of Spain |- |Prince Ludwig Ferdinand of Bavaria||1859||1949|| |- |rowspan=2|1860||Antonio Remón Zarco del Valle y Huet||1785||1866|| |- |Mariano Téllez Girón, 12th Duke of Osuna and Infantado||1814||1882|| |- |1861||Luís I, King of Portugal||1838||1889|| |- |rowspan=2|1862||Frederick, Crown Prince of Prussia||1831||1888||later German Emperor Frederick III |- |Francisco, Duke of Marchena||1861||1923|| |- |rowspan=2|1863||Louis III, Grand Duke of Hesse||1806||1877|| |- |William Nicholas, Prince of Orange and Crown Prince of the Netherlands||1840||1879|| |- |1864||Christian