Valentine de Riquet de Caraman-Chimay

[3] From her mother's first marriage, she had an elder half-brother, Henri, Marquis of Brigode who was the Mayor of Romilly (and married Annette du Hallay-Coëtquen).

His maternal grandparents were Françoise-Marie LeRoy and wealthy financier Henri de Pellapra, though Émilie claimed to be a daughter of Napoleon.

He was a French general who known for leading the 'Charge de Sedan' alongside Gaston Alexandre Auguste in 1870.

Georges' elder brother, Grégoire (who inherited the Brâncoveanu patrimony), was the father of Princess Catherine Hélène Bibesco-Bassaraba, who married Valentine's nephew, Prince Alexandre de Caraman-Chimay (a son of her brother Joseph, 18th Prince de Chimay).

After they married, Prince Georges and Valentine were the parents of three more children, only two of whom survived to adulthood:[10] The Princess died on 25 August 1914.