Prince of Asturias (Charles IV of Spain) |- |1784||Infante Ferdinand of Spain||1784||1833||later King Ferdinand VII of Spain. Head of the order from 1808 |- |rowspan=5|1785||José, Prince of Brazil||1761||1788||son of Queen Maria I of Portugal |- |Infante John of Portugal||1769||1826||later King John VI of Portugal |- |Henri de Meneses, Count of Ericeyra and Marquis de Lourizal||?||?|| |- |Philippe Louis Marc de Noailles, Prince of Poix||1752||1819|| |- |Joaquín Antonio de Palafox y Rebolledo, Marquis of Ariza||?||1775|| |- |1786||Infante Peter Charles Anthony of Spain||1786||1812||son of Gabriel de Borbón |- |rowspan=2|1788||Infante Carlos of Spain||1775||1855||First Carlist Claimant to the Throne of Spain |- |Prince Carlo Gennaro||1788||1789||son of King Ferdinand I of the Two Sicilies |- |rowspan=16|1789||Infante Charles John of Spain||1788||1789||son of Gabriel de Borbón |- |||1727||1798|| |- |Salatore Montaperto Uberti Branciforte, Prince of Raffadali||?||1801|| |- |Manuel José Pacheco Téllez Girón y Toledo||1732||1794|| |- |Cristobal Pío Funes de Villapandro, Count of Atares||?||?|| |- |Pedro Francisco Lujan Silva, Duke of Almodóvar||1727||1789|| |- |Judas Tadeo Fernández de Miranda, 5th Marquis of Valdecarzana||?||1810|| |- |Juan de Silva Rabatta, 14th Count of Cifuentes||?||1792|| |- |Paul François de Quélen, Prince of Carency and Duke of Vauguyon||1746||1728|| |- |||1749||1806|| |- |Vicente Joaquín Osorio de Moscoso, 15th Marquis of Astorga, 11th Count of Altamira, Prince of Aracena and Duke of Sesa||1756||1816|| |- |Juan Pablo de Aragón Azlor y Zapata de Calatayud, 11th Duke of Villahermosa, Duke of Palata and Count of Real||1730||1790|| |- |Louis Henri, Duke of Bourbon||1756||1830|| |- |Charles Roger, Prince of Bauffremont-Listenois||1713||1795|| |- |Andrea IV Doria-Pamphili-Landi, Marquis of Torriglia and Melfi||1747||1820|| |- |||1743||1803|| |- |rowspan=3|1790||Diego Fernández de Velasco, 13th Duke of Frías and Uceda, Count of Alba and Lista||1754||1811|| |- |Diego de Noronha||?||?|| |- |Joseph Anne Auguste, Duke of Croy-Havré||1744||1839|| |- |rowspan=5|1791||Francesco Augusto Cattaneo, Duke of Termoli and 4th Prince of San Nicandro||1721||1791|| |- |José Álvarez de Toledo, Duke of Alba, 15th Duke of Medina Sidonia, 11th Duke of Montalto, 10th Duke of Bivona, 8th Duke of Fernandina||1756||1796|| |- |José Monino, Count of Floridablanca||1728||1808|| |- |Aususto Cattaneo, Duke of Termoli and 5th Prince of San Nicandro||1754||1824|| |- |Infante Philip Maria of Spain||1792||1894||son of King Charles IV of Spain |- |rowspan=2|1792||Maximilian, Prince of Saxony||1759||1838|| |- |Manuel de Godoy, Prince of the Peace||1767||1851|| |- |rowspan=7|1794||Infante Francisco de Paula of Spain||1794||1865||son of King Charles IV of Spain |- |Carlo Sebastiano Ferrero Fieschi, Prince of Masserano||1760||1826|| |- |Vicente María de Palafox, Marquis of Ariza||?||?|| |- |Vicenzo Maria de Vera Aragon, Duke of la Rocca||?||?|| |-