On his birth in 1847, Grand Duke Vladimir Alexandrovich was appointed to the Life Guards of the Preobrazhenskii Regiment.  He began his military career as an ensign in 1854.  The following year, he entered the Life Guards Rifle Battalion.  He later took command of the First Battalion of the Life Guards of the Preobrazhenskii Regiment (from 1867 to 1868), served as Major-General of His Imperial Majesty’s Suite (1868), and in that same year was appointed a Senator (1868).  Subsequently he took general command of the Life Guards of the Preobrazhenskii Regiment (1869), was appointed Adjutant-General (1872), and a Member of the State Council (from 1872 to 1906).

On August 16/29, 1874, Grand Duke Vladimir Alexandrovich married in St. Petersburg Princess Marie-Alexandrine-Elisabeth-Eleonore of Mecklenburg-Schwerin (who, upon becoming a member of the Russian Imperial House, took the title and name Grand Duchess Maria Pavlovna).  Grand Duchess Maria Pavlovna was the daughter of Grand Duke Friedrich-Franz II (1823-1883) of Mecklenburg-Schwerin and his wife, Grand Duchess Augusta (née Princess of Reuss-Kröstritz).

The couple had five children:  Grand Duke Alexander, Emperor-in-Exile Kirill I, Grand Duke Boris, Grand Duke Andrei, and Grand Duchess Elena, Princess of Greece and Denmark. 

In the same year that he married, Grand Duke Vladimir Alexandrovich was promoted to the rank of Lieutenant-General (1874).  He served in the Russo-Turkish War of 1877-1878, as the President of Imperial Academy of Art (1876), and later took a senior administrative position in the Guards Corps and of the St. Petersburg Military District (1881). He then took overall command of the Guards Corps and of the St. Petersburg Military District (1884), and later was appointed to the Council of Ministers (1892).

His Honours include the Imperial Order of St. George III Class (received on November 14/27, 1877).  In 1903, he was appointed Chairman of the Knights’ Council of the Imperial Order of St. George. 

Grand Duke Vladimir Alexandrovich retired in 1905.  He was well known for his charity work, and for his patronage of the sciences, the arts, and sports.  He was widely regarded as a man of enormous experience in State affairs, wise and measured in his judgments, and of great personal style and taste. 

He was buried in the New Mausoleum of the House of Romanoff in the Ss. Peter and Paul Cathedral in the Ss. Peter and Paul Fortress, St. Petersburg. 

Among the Righteous, O Lord, grant eternal rest to the pious Grand Duke Vladimir Alexandrovich, and may his memory be eternal.