[1] Pauline Therese was born in Riga, one of the five children of Duke Louis of Württemberg and his wife, Princess Henriette of Nassau-Weilburg.

Her siblings included Maria Dorothea, Archduchess of Austria; Amelia, Duchess of Saxe-Hildburghausen; Elisabeth Alexandrine, Princess of Baden, and Duke Alexander of Württemberg himself the founder of the Teck branch of the family.

Her paternal grandparents were Frederick II Eugene, Duke of Württemberg, and Friederike Dorothea of Brandenburg-Schwedt.

As his third wife, their marriage was unhappy, particularly because of the deep attachment William showed to his mistress, the actress Amalia Stubenrauch.

In a letter written to her friend Lady Malet, Queen Sophie would later write of the possibility of how her stepmother Queen Pauline and one of her daughters (Catherine or Augusta) would soon be taking refuge in the Netherlands, as a consequence of the events following the Revolutions of 1848 in the German states.