Leopoldine was the fourth and youngest daughter of Prince William of Baden (1792-1859) and Duchess Elisabeth Alexandrine of Württemberg (1802-1864), daughter of Duke Louis of Württemberg.

Her paternal grandparents were Charles Frederick of Baden, the first Grand Duke of Baden, and his second wife, Baroness Louise Caroline Geyer of Geyersberg, Countess of Hochberg.

She grew up in Karlsruhe, together with her two older sisters, Sophie (1834-1904) and Elizabeth (1835-1891).

In Strasbourg, where her husband was appointed as the Governor of Alsace-Lorraine, she took mainly ceremonial duties.

She died the day before Christmas Eve 1903, after a long illness.