[citation needed] On 26 August 1873 at Friedrichshafen, Baden-Württemberg, Pauline married Charles Augustus, Hereditary Grand Duke of Saxe-Weimar-Eisenach.

[1] They were second cousins, as she was the paternal granddaughter of Prince Bernhard, younger brother of the Charles Frederick, Grand Duke of Saxe-Weimar-Eisenach, the grandfather of Karl August.

[citation needed] She continued to be styled as Dowager Hereditary Grand Duchess only by courtesy, as she was unpopular with her family and her son's subjects.

[citation needed] Though she lived much of her widowhood away from the Saxe-Weimar court, Pauline "contributed even from a distance, to create the difficulties which rendered the position of her daughter-in-law, the present Grand Duchess, so extremely difficult during the first few months of marriage".

[citation needed] She was described as "extraordinarily fat, and one of the most plain-featured princesses of Germany, her homeliness being of the crabbed and sour order rather than of a genial nature".