Reductive functionalization of CO2 with amines and a reductant, which combines both reduction of CO2 and C–N bond formation in one pot to produce versatile chemicals and energy-storage materials such as formamides, aminals, and methylamines that are usually derived from petroleum feedstock, would be appealing and promising. Herein, we give a brief review on recent developments in the titled CO2 chemistry by employing transition-metal-free catalysis, which can be catalogued as below according to the diversified energy content of the products, that is formamides, aminals, and methylamines being consistent with 2-, 4-, and 6-electron reduction of CO2, respectively. Notably, hierarchical reduction of CO2 with amines to afford at least two products, for example, formamides and methylamines, could be realized with the same catalyst through tuning the hydrosilane type, reaction temperature, or CO2 pressure. Finally, the opportunities and challenges of the reductive functionalization of CO2 with amines are also highlighted.1 Introduction2 2-Electron Reduction of CO2 to Formamide3 6-Electron Reduction of CO2 to Methylamine4 4-Electron Reduction of CO2 to Aminal5 Hierarchical Reduction of CO2 with Amines6 Conclusion