Russia, an economically diverse and vast country, is the world’s major fossil-fuel supplier and the fourth-largest CO2 emitter. Understanding subnational CO2 emission patterns and the determinants driving these patterns are essential for Russia to be able to differentiate emission reduction measures. However, due to the lack of systematic statistics, Russia’s subnational CO2 emissions and their driving factors are still unknown. To fill this knowledge gap, we propose a method to estimate the energy-related and process-related CO2 emissions of Russia’s 80 constituent entities from 2010 to 2017. According to different economic structures, the 80 constituent entities are then classified into commercial, industrial and mixed-economy groups. Additionally, the driving forces of the 80 constituent entities’ CO2 emissions within corresponding groups are discussed and compared using the logarithmic mean Divisia index method. We find that: (1) the 80 constituent entities display great inequality in CO2 emission levels, primarily because of their large variety in socio-economic development. Tyumen region discharged the highest amount of CO2 emissions in 2017, at 138.34 Mt, followed by Moscow city (76.00 Mt), while the Jewish autonomous region has the lowest level at a mere 0.92 Mt; and (2) driving mechanisms of CO2 emissions changed dynamically and varied by groups around the occurrence of Russia’s 2014 political and economic crisis. Economic expansion and energy intensity played a dominant role in raising and inhabiting CO2 emissions for all groups respectively, though, after the crisis, the industrial structure and energy intensity became the main drivers of increasing emissions for commercial and industrial groups, respectively. The emission construction method and database provide a basis for further emission-related studies at the subnational level, while the driving forces analysis and low-carbon roadmaps provide references for other developing countries with high levels and inequalities in emissions as they seek to achieve sustainability.