Since his youth, his mother served as governess of the younger children of the then Grand Duke Paul Petrovich of Russia, Heir-Apparent to the throne of the then Empress Catherine II.
In 1797, Emperor Paul I made him his aide-de-camp, and in 1798 he was promoted to the rank of Major-general and assigned to the post of the Director of the Mobile Field Chancellery (военно-походная канцелярия) of His Majesty.
He was somewhat overshadowed by his more illustrious wife, the famous socialite and political force, Dorothea Lieven, née Countess von Benckendorff (17 December 1785, Riga – 27 January 1857, Paris), whom he had married on February 1, 1800 in St. Petersburg.
Together they had one daughter and five sons: Magda, Paul (24 February 1805 – 1866), Alexander (9 March 1806 – 5 October 1885), Konstantin (1807–1838), Georg and Arthur.
Lieven died suddenly on January 10, 1839 at Rome as he escorted the future Alexander II of Russia on his Grand Tour.