Her father was Prince Grégoire Bibesco-Bassaraba, a son of Wallachian Prince Gheorghe Bibesco and Zoe Mavrocordato-Bassaraba de Brancovan.
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Born Princess Anna Elisabeth Bibesco-Bassaraba de Brancovan in Paris, she was a descendant of the Bibescu and Craioveşti families of Romanian boyars.
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Via her mother, Anna de Noailles is a great-great-granddaughter of Sophronius of Vratsa, one of the leading figures of the Bulgarian National Revival, through his grandson Stefan Bogoridi, caimacam of Moldavia.
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Together with Elena Văcărescu, Anna de Noailles, and Marthe Bibesco, Elvira Popescu is considered to be the inspiration for Henri Matisse's painting, La Blouse Roumaine (1940).
As a fashionable portraitist, he was commissioned for subjects including Arletty, Louis Barthou, Sacha Guitry, Leopold III of Belgium, Anna de Noailles and Maurice Chevalier.