After briefly attending Moscow University, he joined the Army to fight against Napoleon, thereby beginning a military career that would last the rest of his life.
During the 1831 November Uprising in Poland, Annenkov served as Chief of Staff to General Baron Fabian Gottlieb von Osten-Sacken.
[3] Annenkov was a co-founder, in 1856, of the Moscow-Saratov Railway with General Semyon Alexeievich Yurievich, Paul von Derwies, and the Privy Councilors M.N.
His final posting, from 1862 to 1865, was as Governor-General of Kiev and the western provinces; however, illness cut short his service, and he retired to Nice, France, for recuperation.
General Nicholas Annenkov was married to Vera Ivanova Bukharina (1813–1902), daughter of Ivan Bukharin (1772–1858), Governor-General of Kiev (1820–22).