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On 21 August 1702 Antonio took the oath to King Louis XIV of France in the Parlement on account of being Duke of Valentinois and a Peer of France.
Born at the Château de Kerscamp, Hennebont, Morbihan, France, as Count Pierre Marie Xavier Raphael Antoine Melchior de Polignac, he was the fourth son and youngest child of Count Maxence Melchior Edouard Marie Louis de Polignac (1857–1936) and his Mexico-born wife whom he wed in Paris in 1881, Susana Mariana Estefanía Francisca de Paula del Corazón de la Torre y Mier (1858–1913).
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According to James Lees-Milne, a British writer and friend of the Prince, Prince Pierre's unhappy arranged marriage was complicated by his homosexuality and Princess Charlotte's affairs.