Vladimir Orlov-Davydov was born in St. Petersburg in 1837. He was baptized along with his twin brother Anatoly in St. Isaac’s Cathedral. Vladimir received a good home-school education. In 1855, he was enlisted in the military service as a non-commissioned officer in the 4th Division of the Chevalier Guard Regiment. The next year, he was promoted to cornet and then transferred to the army group operating in the Caucasus.

In the Caucasus, Vladimir Orlov-Davydov took part in constant clashes with the local guerillas. In 1859, he was promoted to lieutenant and transferred as a special assignments officer to his uncle, the commander-in-chief of the Caucasus Army, Field Marshal General Prince Alexander Baryatinsky. In 1860, as the captain commanding the 3rd Company of the 20th Rifle Battalion, he was decorated with the 3rd-class Order of St. Stanislaus with swords and a bow for his distinction in the military operation against the mountain guerillas. In the same year, during an attack on the hamlet of Benoy, he was seriously wounded.

In 1861, Orlov-Davydov was transferred to the Chevalier Guards Regiment as a captain while at the same time being appointed adjutant to the commander-in-chief of the Caucasus army. In 1863, he was again transferred to the Kabardin Infantry Regiment with simultaneous promotion to lieutenant colonel. In 1864, the count was appointed aide-de-camp, promoted to colonel, and sent as a courier to London. Returning to Russia, in 1865, he went to the Voronezh Governorate to observe the recruitment of new soldiers, and several times he traveled back to the Caucasus to Grand Duke Mikhail Nikolaevich on various assignments.

In 1866, Orlov-Davydov was promoted to major general and appointed to the retinue, and then he was named the governor of Simbirsk (1866–1868). There, he oversaw the renovation of the city after the devastating fire of 1864: this included the construction of the first city-wide water supply system as well as the opening of the first Chuvash school for teachers.

In 1868, Vladimir Orlov-Davydov stepped down as the governor and got a position with the Ministry of Internal Affairs, while also remaining an official member of the royal retinue. He died of illness on the island of Corfu on April 7, 1870. For his services to his country and the crown over the years, he was awarded the 3rd-class Order of St. Anna with swords and a bow, the 3rd-class Order of St. Stanislaus with swords and a bow, the 4th-class Order of St. Vladimir with swords and a bow, and the 3rd-class Order of St. Vladimir with swords over it.