Hermine was the only daughter of Archduke Joseph, Palatine of Hungary by his second wife, Princess Hermine of Anhalt-Bernburg-Schaumburg-Hoym, daughter of Prince Victor II of Anhalt-Bernburg-Schaumburg-Hoym and Princess Amelia of Nassau-Weilburg.

Her mother died shortly after giving birth to her and her twin brother, Archduke Stephen, Palatine of Hungary.

She spent much of her childhood in Buda and at the family estate in Alcsútdoboz and received an excellent education.

However, she was a slim young woman, with frail body, and prone to diseases.

In 1837 she became Princess-Abbess of the Theresian Royal and Imperial Ladies Chapter of the Castle of Prague (1835-1842).