Her first marriage was to Prince Paul de Bauffremont-Courtenay (1827–1893) on 13 April 1861. He was a French general who known for leading the 'Charge de Sedan' alongside Gaston Alexandre Auguste in 1870. Before their divorce in 1875, they were the parents of two daughters:[7]
Princess Catherine-Marie-Josèphine de Bauffremont-Courtenay (1862–1932),[7] who married diplomat Nicolas Wlassow, in Bucharest in 1888.[8]
Princess Jeanne-Marie-Émilie de Bauffremont-Courtenay (1864–1935), who married Don Luigi Sanfelice, Principe di Viggiano, Marchese di Monteforte.[9]
Before her divorce, she gave birth to a daughter, Marcela, she conceived with Romanian Prince Georges Bibescu. After their divorce, she gained custody of both children.[10]
Second marriage
In 1875, she married Romanian Prince Georges Bibescu (1834–1902), son of Prince of WallachiaGheorghe Bibescu and, his first wife, Zoe Brâncoveanu. 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]