Archduchess Maria Karoline was born in Vienna as the second daughter and sixth child of Archduke Charles, Duke of Teschen and Princess Henrietta of Nassau-Weilburg. Her father, the "hero of Aspern", was a son of Leopold II, Holy Roman Emperor and Infanta Maria Luisa of Spain. Her mother was a daughter of Frederick William of Nassau-Weilburg (1768–1816) and his wife Burgravine Louise Isabelle of Kirchberg. Between her siblings there were Maria Theresa, Queen consort of Two Sicilies and Archduke Albrecht, Duke of Teschen.