Volsky was born into a noble family. His father was an attorney. After he finished the Tambov gymnasium (1894), Volsky entered the Physics and Mathematics Department of Moscow University but was expelled for being involved in student social-democratic organization (November 1897). In 1899 he was exiled to Tambov, in 1902 – to Vyatka governorate. In 1902–1904, he was in exile abroad. In 1903, Volsky joined the Socialist Revolutionary Party (SRP).

In 1904, he returned to Russia and organized Socialist-Revolutionaries (SRs) combat group in Baku. In December 1905, he was arrested in Tambov and exiled to the Vyatka governorate. In 1908, he was exiled to Vologda where he ran the local SRP. Since 1911, he lived in Moscow, where he was engaged in organizing Socialist-Revolutionaries (SRs) combat groups. During the World War I, he headed SRP in Tver. In 1916 he was briefly exiled to Kashyn and Kostroma.

In 1917, he was the Chairman of the Tver SRP Governorate Committee and the Tver Governorate Zemstvo Council. He was also a leader of the Tver Soviet of Workers’ and Soldiers’ Deputies. He was elected an MP (deputy) of the Constituent Assembly.

After the October coup of 1917, the SRP Central Committee sent him to the Volga region and the Urals to fight the Bolsheviks. After the organization of the Committee of Members of the Constituent Assembly (Komuch) based in Samara, Volsky became its member (June 8) and later Chairman (July to September 1918). He took part in the Ufa State Conference (September 1918). In September–November 1918, Volsky chaired the Congress of Members of the All-Russian Constituent Assembly.

Upon Kolchak’s coup, on November 18, 1918, in Omsk, he published a proclamation “To all the peoples of Russia” urging people to fight against the power of Aleksander Kolchak. He was arrested in Yekaterinburg, fled from prison, and joined the anti-Kolchak underground.

Since early 1919, the so-called Ufa delegation, i.e., a group of SRP Central Committee’s members (Konstantin Burevoy, Vladimir Volsky, Nikolay Rakitnikov, and others) launched negotiations with the Bolsheviks to discuss joint action against Kolchak and formed the Narod [People] group. In the autumn of 1919, the SRP Central Committee decided to dissolve the group, under the threat of expelling its members from the Party. So, the Narod members announced their withdrawal from the SRP and established an independent organization named the Minority Party of Socialist-Revolutionaries (MPSR). Volsky became a member of the MPSR’s Central Organizational Bureau. He advocated the expansion of democratic freedoms in the Russian SFSR (universal suffrage, freedom of speech, press, assembly for the workers and parties that are not fighting against the Soviet regime).

In 1921, during the Kronstadt rebellion, he became a member of the Political Center, a body designed to take over the political leadership of the rebellion, according to the plan of its organizers. It should be noted that this action had not been coordinated with the MPSR’s leadership. In 1922, Volsky was arrested and exiled. In 1937, he was arrested again and sentenced to death over his alleged involvement in an anti-Soviet terrorist organization. He was rehabilitated in 1991.