He graduated from the Pavel Military School in Saint Petersburg, opting to serve in the Orenburg Cossack Regiment.

In protest against the harsh treatment of the civilian population by General Mikhail Skobelev, Nalivkin resigned from the military and entered civil government, where he was placed as the assistant head of the Fergana Valley region.

Between 1878 and 1884, Maria Nalivkina learned the local language and gained an intimate insight into the lives of ordinary Sart women.

Nalivkin was later appointed as the head of the Turkestan Committee of the Provisional Government set up shortly after the annexation of the territory into the Russian Empire was complete, and represented the capital Tashkent in the Imperial State Duma.

Despite being a member of the Imperial Duma, Nalivkin was initially sympathetic to the revolution and the Provisional Government, believing it would bring improvements to quality of life among the people of the empire.