She was the eldest daughter of Adolf, Hereditary Prince of Schaumburg-Lippe and his wife Princess Hermine of Waldeck and Pyrmont.

[1] Despite their high birth, Princess Hermine and her siblings were brought up very simply; one report said they "knew more about the kitchen than many women of lower degree".

[2] They were also well educated, and were able to hold their own in discussions about philosophy and science with the learned men in the principality.

[2] On 16 February 1876, Hermine married Duke Maximilian of Württemberg, a son of the German naturalist and explorer Duke Paul Wilhelm of Württemberg and Princess Maria Sophia of Thurn and Taxis.

Duke Paul Wilhelm was a member of the ducal and Silesian branch of the House of Württemberg.