After returning from Switzerland, where she had obtained medical training, Figner became a member of the Land and Liberty group, which soon splintered into two groups. Of the two, Figner joined the People's Will group, which was much more radical and advocated terrorism. After several members of People's Will were arrested, Figner became its leader. She was involved in many terrorist activities including the March 1, 1881 assassination of Alexander II, son of Tsar Nicholas I. After being on the run for some time, gaining infamy as the most hunted revolutionary in Russia, she was arrested in 1883. At first she was sentenced to death but this was commuted to life imprisonment in Siberia.
In 1904, after serving over twenty years, Figner was released from prison and quickly joined the Socialist Revolutionaries, but she soon left after discovering one of its members, Evno Azef, was a secret agent.
In the 1920s, Figner published an autobiography, Memoirs of a Revolutionist. She was active in radical politics and remained under Cheka surveillance until she died in 1942.