LAUSR

Abstract Electroreduction of carbon dioxide into value‐added fine chemicals is a promising technique to realize the carbon cycle. Recently, metal‐free heteroatom doped carbons are proposed as promising cost‐effective electrocatalysts for CO2 reduction reaction (CO2RR). However, the lack of understanding of the active site prevents the realization of a high‐performance electrocatalyst for the CO2RR. Herein, we synthesized metal‐free N, P co‐doped carbons (NPCs) for producing syngas, which is composed of H2 and CO, by CO2 electrolysis using inexpensive bio‐based raw materials via simple pyrolysis. The syngas ratio (H2/CO) can be controlled within the high demand range (0.3–4) at low potentials using NPCs by tuning the N and P contents. In comparison with only N doping or P doping, N and P co‐doping has a positive impact on improving CO2RR activity. Experimental analysis and density functional theory (DFT) calculations revealed that negatively charged C atoms adjacent to N and P atoms are the most favorable active sites for CO2‐to‐CO conversion compared to pyridinic N on N, P co‐doped carbon. Introducing N atoms generates the preferable CO2 adsorption site, and P atoms contribute to decreasing the Gibbs free energy barrier for key *COOH intermediates adsorbed on the negatively charged C atoms.