In 1892-1907, the chemist D. I. Mendeleev served as head of the Main Chamber of Weights and Measures, the first national metrology institution in the Russian Empire. In conjunction with other reforms carried out and planned by the Finance Ministry, he was actively involved in preparing the switch to the international metric system. This study analyses Mendeleev's approach and strategy for introducing metrology reform in Russia, his interaction with state officials such as S. Yu. Witte and V. I. Kovalevsky, and his 1899 legislative proposal on «The Regulation on Measures and Weights.» The article further describes the scientific and organizational principles on which Mendeleev founded the Chamber's practical work, its scientific equipment, the construction of the building for experimental investigations in metrology, and the establishment of an astronomical department and special clock.