In 1867, he co-founded the 'One Rouble Society' with German Lopatin; it was dedicated to propaganda and educational work among the masses.

One of the members of Volkhovsky's Odessa group was Andrei Zhelyabov, later one of the principal organisers of the assassination of Tsar Alexander II.

After escaping from Siberia, he made his way to Western Europe, eventually settling in London.

He worked for the Free Russian Press and was a close friend and collaborator of the revolutionary writer S.M.

He also did his best to represent the Russian opposition movement to the West, maintaining contacts with British, French and German socialist parties, contributing articles to British and Americal papers (including The New York Times) and writing pamphlets aimed at the Western audience.