The rapid increase of the CO2 concentration in the Earth's atmosphere has resulted in numerous environmental issues, such as global warming, ocean acidification, melting of the polar ice, rising sea level, and extinction of species. To search for suitable and capable catalytic systems for CO2 conversion, electrochemical reduction of CO2 (CO2RR) holds great promise. Emerging heterogeneous carbon materials have been considered as promising metal‐free electrocatalysts for the CO2RR, owing to their abundant natural resources, tailorable porous structures, resistance to acids and bases, high‐temperature stability, and environmental friendliness. They exhibit remarkable CO2RR properties, including catalytic activity, long durability, and high selectivity. Here, various carbon materials (e.g., carbon fibers, carbon nanotubes, graphene, diamond, nanoporous carbon, and graphene dots) with heteroatom doping (e.g., N, S, and B) that can be used as metal‐free catalysts for the CO2RR are highlighted. Recent advances regarding the identification of active sites for the CO2RR and the pathway of reduction of CO2 to the final product are comprehensively reviewed. Additionally, the emerging challenges and some perspectives on the development of heteroatom‐doped carbon materials as metal‐free electrocatalysts for the CO2RR are included. Emerging heterogeneous carbon materials are considered as promising metal‐free electrocatalysts for the electrochemical CO2 reduction reaction (CO2RR) with remarkable catalytic activity, long durability, and high selectivity. Various carbon materials with heteroatom doping as metal‐free catalysts for the CO2RR are highlighted, and recent advances on the identification of active sites for the CO2RR and the pathways for reduction of CO2 to the final product are comprehensively reviewed.