Blanca married Archduke Leopold Salvator of Austria, second child and eldest son of Archduke Karl Salvator of Austria and his wife Princess Maria Immaculata of Bourbon-Two Sicilies, on 24 October 1889 at Schloss Frohsdorf in Lanzenkirchen, Lower Austria, Austria.
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After the defeat of Austria-Hungary in World War I in 1918 and the fall of the Habsburg dynasty, Archduchess Blanca with her husband and their children refused to recognize the new Austrian republic.
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Blanca was forced to ask permission to live in Barcelona to her cousin Alphonso XIII of Spain, who belonged to the rival branch of the Spanish Bourbons.
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The family left Austria after the end of the Monarchy and finally settled in Barcelona.
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