Perovskaya was born in Saint Petersburg, into an aristocratic family who were the descendants by the marriage of Elizabeth of Russia.

[1] After the family moved to Saint Petersburg, Perovskaya entered the Alarchinsky Courses, a girls’ preparatory program.

A prominent fellow member of the Circle of Tchaikovsky, Peter Kropotkin, said the following of Perovskaya: In her moral conceptions she was a "rigorist", but not in the least of the sermon-preaching type.

"[1]In 1873, Perovskaya maintained several conspiracy apartments in Saint Petersburg for secret anti-tsarist propaganda meetings that had not been sanctioned by the authorities.

Perovskaya also took part in an unsuccessful attempt to free Ippolit Myshkin, a revolutionary and a member of Narodnaya Volya.

She was the closest friend and later the wife of Andrei Zhelyabov, a member of the executive committee of Narodnaya Volya.

[6][3] Perovskaya would later relate that, before heading to the Catherine Canal, she, Rysakov and Hryniewiecki sat in a confectionery store located opposite of the Gostiny Dvor, impatiently waiting for the right time to intercept Alexander II's cavalcade.

[6] In the afternoon, the Tsar was returning by Catherine Canal in his carriage after watching the weekly military roll call.

[8] The autocrat survived this first action because his carriage was bulletproof but the second bomb, thrown by Ignacy Hryniewiecki, dispatched him.

[9] [10] Just before her trial, she wrote in a letter to her mother: My darling, I implore you to be calm, and not to grieve for me; for my fate does not afflict me in the least, and I shall meet it with complete tranquility, for I have long expected it, and known that sooner or later it must come.

[11]Perovskaya, along with the other conspirators were tried by the Special Tribunal of the Ruling Senate on 26–29 March and sentenced to death by hanging.

[16] Three decades after her death, Perovskaya would become the inspiration for the Japanese feminist Kanno Sugako, who was involved in a 1910 plan to assassinate the Emperor Meiji.