[citation needed] Pauline married Friedrich Hermann Otto, Hereditary Prince of Hohenzollern-Hechingen, on 26 February 1800 in Prague.

She separated from her spouse in 1805, after an affair with her brother-in-law Prince Louis de Rohan-Guémenée (1768–1836).

[citation needed] During the Vienna Congress of 1815, she had an affair with General Ludwig von Wallmoden-Gimborn which attracted attention.

[citation needed] In 1838, she inherited the Duchy of Sagan after the death of her sister.

[citation needed] She spent the last years of her life together with her sister Princess Joanna of Courland in Vienna.