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 Helena, she was one of the candidates to marry King William III of the Netherlands.

Pauline was already in love with Crown Prince Alexis of Bentheim and Steinfurt and she refused to marry the monarch.

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.