He was arrested, imprisoned and deported because of his revolutionary activities after the 1905 Revolution. In 1907 he escaped from prison and fled to France. He settled in Paris where he completed his studies, came under the influence of Russian anarchists and joined the movement, a small group of Apollon Karelin, in 1911. Volin's views eventually gravitated towards anarcho-syndicalism, and he decided to leave the Socialist-Revolutionary Party in 1913. During the first months of the First World War he participated in the International Commission for the Anti-militarist Section, for which he was detained by the French authorities in 1915. At this point he was married and had four children. He remained in a concentration camp from where he was to be deported, but he escaped with the help of some French comrades and embarked from Bordeaux to the United States.