Throughout her life, Louise remained very close to her first cousin, Archduchess Marie Valerie of Austria.

She was the daughter of the French prince Ferdinand, Duke of Alençon, and his wife Duchess Sophie Charlotte in Bavaria.

Louise's mother was a sister of Empress Elisabeth of Austria ("Sisi") and Queen Marie of the Two Sicilies, the heroine of Gaeta.

On 15 April 1891 at Schloss Nymphenburg, Louise married her second cousin Prince Alfons of Bavaria.

They had two children: In Paris on 4 May 1897, her mother, the famed duchesse d'Alençon, died in a fire at a charity bazaar (the Bazar de la Charité); she had refused rescue attempts, insisting that the girls working with her at the bazaar be saved first.