[4] Samoilova's father was an Orthodox priest in Irkutsk, Siberia, and she had a sister, Kaleriia.

She took part in her first demonstration in February 1897 while a university student, studying Bestuzhev Courses in St. Petersburg.

She returned home to Irkutsk until early 1902, when she received a passport and left for Paris to study Marxism at the Vol'naaia Russkaia shkola obshchestvennykh nauk (Free Russian School of Social Sciences) where the lecturers included Vladimir Lenin and Julius Martov and eventually joined their newspaper Iskra as a journalist.

In 1903, she joined the Russian Social Democratic Labour Party (bolsheviks) or RSDLP(b).

At the First All-Russian Women's Congress in November 1918, she sat on the podium with Inessa Armand, Alexandra Kollontai, and Klavdiia Nikolaeva.