Pauline was born in Arolsen, Principality of Waldeck and Pyrmont on 19 October 1855 and was the second-eldest child and daughter of George Victor, Prince of Waldeck and Pyrmont and his first wife Princess Helena of Nassau. Pauline was an elder sister of Marie, Crown Princess of Württemberg, Emma, Queen of the Netherlands, Helena, Duchess of Albany, Friedrich, Prince of Waldeck and Pyrmont, and Elisabeth, Princess of Erbach-Schönberg.

Together with her sisters Emma and Elena, she was one of the candidates to marry King William III of the Netherlands. In the summer of 1878, she arrived in Arolsen to choose one of them. Pauline was already in love with Crown Prince Alexis of Bentheim and Steinfurt and she refused to marry the monarch. Her sister Emma became queen of the Netherlands.

Shortly before her 26th birthday, she married the 35-year-old Alexis on May 7, 1881 in Arolsen.^[1] The family received the title of princes in 1817. During the mediatization of 1806, the lands of their county were included in the Grand Duchy of Berg and, later, in the Kingdom of Prussia . However, the head of the family remained a member of the House of Lords of the Landtags of Prussia and Württemberg.

Pauline married Alexis, Hereditary Prince of Bentheim and Steinfurt, fourth child and eldest son of Ludwig Wilhelm, Prince of Bentheim and Steinfurt and his wife Landgravine Bertha of Hesse-Philippsthal-Barchfeld, on 7 May 1881 in Arolsen, Principality of Waldeck and Pyrmont, the newlyweds settled in Bentheim Castle.^{[citation needed]} Pauline and Alexis had eight children:

• Prince Eberwyn of Bentheim and Steinfurt (10 April 1882 – 31 July 1949)

∞ 1906–1914 Pauline Langenfeld (1884–1970)

∞ 1918–1919 Ellen Bischoff-Korthaus (1894–1936), who later remarried Adolf II, Prince of Schaumburg-Lippe

∞ 1920 Anne-Louise Husser (1891–1951)

• Victor Adolf, Prince of Bentheim and Steinfurt (18 July 1883 – 4 June 1961)

∞ 1920 Princess Stephanie of Schaumburg-Lippe (1899–1925)

∞ 1931 Princess Rosa Helene of Solms-Hohensolms-Lich (1901–1963)

• Prince Karl Georg of Bentheim and Steinfurt (10 December 1884 – 14 February 1951)

∞ 1914 Princess Margarete of Schönaich-Carolath (1888–1980)

• Princess Elisabeth of Bentheim and Steinfurt (12 July 1886 – 8 May 1959)
• Princess Viktoria of Bentheim and Steinfurt (18 August 1887 – 30 January 1961)
• Princess Emma of Bentheim and Steinfurt (19 February 1889 – 25 April 1905)
• Prince Alexis Rainer of Bentheim and Steinfurt (16 December 1891 – 30 June 1923)
• Prince Friedrich of Bentheim and Steinfurt (27 May 1894 – 17 May 1981)