In 1795, married to Dmitry Lvovich Naryshkin (a hofmeister). In 1799, she entered into a relationship with Alexander, who became tsar in 1801, with her spouse"s approval. She was well liked by Alexander"s family, except by his consort, the empress Elizabeth Alexeyevna.
She is described as fascinating and charming, with the ability to attract people, and called "The Aspasia of the North".
In 1803, she made an attempt to have Alexander divorce his spouse and marry her, but failed. She accompanied the tsar to the Vienna Congress in 1815, which gave him bad publicity.
She had at least four illegitimate daughters by Alexander. Three of them (two named Yelizaveta and Zinaida) died in infancy, and the other, Sofia, lived to aged 16.
Her children were:
Marina Naryshkina (1798 – 11 August 1871).
Yelizaveta Naryshkina (born and died 1803). Yelizaveta Naryshkina (born and died 1804). Zinaida Naryshkina (1806 – 18 May 1810).
Sofia Naryshkina (1808 – 18 June 1824).
Emanuel Naryshkin (30 July 1813 – 31 December 1901). Alexander was persuaded to leave her in 1818 and went back to his Elizabeth.
He continued to talk of her as his family.