The daughter of a Moscow lawyer, she was a beautiful girl who first married at 16 to Sawa Mamontov, the music director of the Bolshoi Theatre. She soon divorced him and married Captain Wulfert, an army officer serving in the Regiment of Cuirassiers under Grand Duke Mikhail Alexandrovich Romanov, (1878-1918) brother of Tsar Nicholas II.
Natalia was twenty eight years old when she met Grand Duke Mikhail Romanov, and it was said to be love at first sight for both parties. They soon became inseparable lovers, and the Grand Duke wrote to his brother the Tsar, as required, requesting his permission for them to marry. Not only because Natalia was divorced but also because she was not of Royal blood, the Tsar refused to approve the marriage. For some time Grand Duke Mikhail lived with Natalia, and she gave birth to a son, Georgi on July 24, 1910.
Eventually Mikhail ignored his brother's decree and, in a great love story, secretly married Natalia in Vienna on October 15, 1911 in a Serb Orthodox Church. The significance of the venue was that this marriage could not be put aside by Tsar Nicholas or the Russian Orthodox Church. She and Mikhail were then exiled to England in disgrace. Upon the outbreak of WWI, Mikhail Alexandrovich requested Nicholas' permission to return home and return to the army, with the understanding his wife and children would certainly come too. He returned home to prove himself to be one of Russia's greatest generals, earning the Military's highest honor, the St.George Cross. He, unlike his brother the Tsar, was a great military leader.
In March 1917 after Nicholas abdicated in his favor, Grand Duke Mikhail refused to succeed his brother as Tsar until it was decided by the will of the people. Unfortunately, the people's will would never be heard. Mikhail and his family were first placed under house arrest in Gatchina, then later Mikhail was exiled to the remote city of Perm. Mikhail manage to smuggle his son and step-daughter out of the country to join his mother's family in Denmark, and later Natalia obeyed her husband's order and escaped from Russia with a Danish passport, disguised as a Red Cross nurse. In July 1918, her husband was murdered in Perm, Russia by the Cheka.
Natalia Romanova died in Paris on January 26, 1952 and is buried in Cimetière de Passy in Paris with their only son Georgi Romanov (Prince Brassov), who died at age 21 in an automobile accident on July 22, 1931.