Mai-Maevsky came from a noble family in the Mogilev province, which traced its lineage to the Polish nobility of Maev and Maevski. Both families had the coat of arms "Starykon'", and Vladimir Zenonovich jokingly referred to himself as "the old battle horse". His father served as a staff captain in the Life Guards Jaeger Regiment, and his niece Vera was the wife of the famous polar explorer Georgy Sedov. Mai-Maevsky was born in September 1867 in St. Petersburg, graduated from the cadet corps, the Nikolaev Engineering School, and the Nikolaev Academy of the General Staff. In the Russo-Japanese and First World Wars, he demonstrated leadership abilities and personal bravery. He treated soldiers humanely: after the February Revolution, the soldiers' committee awarded him the Order of St. George, which the general wore alongside the officer's cross.

When the army collapsed due to revolutionary agitation, Mai-Maevsky commanded the 1st Guards Corps on the Southwestern Front. In 1918, he lived in Kyiv, participated in monarchist circles, then moved to the Don and joined the Volunteer Army. After General Mikhail Drozdovsky was wounded, he took command of the 3rd Rifle Division. He gained recognition after battles in the Donbas, where in the spring of 1919, volunteers held back the Red Army's advance on Rostov-on-Don and Novocherkassk.

Colonel Mikhail Levittov described Mai-Maevsky as a man who, despite his corpulence, transformed in combat situations. He paid no attention to bullets and inspired troops to attack.

After successfully repelling the Red Army's offensive in June 1919, the volunteers occupied Kharkiv, and the Kuban Cossacks entered Yekaterinoslav. Mai-Maevsky became the commander of the Volunteer Army and the chief commander of the Kharkiv region. He was gifted a gold saber, and King George V of Great Britain awarded him the Order of Saints Michael and George.

The command of the Armed Forces of Southern Russia decided to advance on Moscow, and the Volunteer Army began its offensive. The capture of Kursk, the advance towards Voronezh, Oryol, Tula, and Bryansk, and the occupation of Little Russia inspired many. Mai-Maevsky sometimes doubted the possibility of a swift capture of Moscow, but he spoke confidently before the troops.

The army needed reserves, and Mai-Maevsky telegraphed Denikin about the difficulties of regrouping. Reinforcements were insufficient, and the volunteers retreated to the Kyiv-Kharkiv line. Despite this, no major part of the army was surrounded and destroyed, which was the merit of Mai-Maevsky and his staff.

The headquarters demanded a resumption of the offensive on Moscow, but this was unrealistic. Mobilization failed, and Mai-Maevsky was removed from his position. He was accused of the collapse of administration, encouraging looting, drunkenness, and other offenses.

Mai-Maevsky's orders stipulated severe punishments for crimes, including execution. He also demanded strict adherence to uniform regulations and a ban on the consumption of alcoholic beverages.

Mai-Maevsky died in the last hours of the White presence in Crimea on November 12, 1920, during the evacuation from Sevastopol. The cause of death is unknown, and the burial place has not been established.