Abstract Carbon-based metal-free catalysts exhibit great applications in electrochemical CO2 reduction (ECR), while most studies merely focus on large-sized carbons with limited ratio of surface atoms for engineering to create surface active centers. Here, we report a joint treatment of C60 by heating and plasma to induce a dramatic performance promotion during ECR. The electrochemical measurements indicate the Faraday efficiency for ECR toward CO production kept at high level over 80% in a wide potential region from − 0.4 to − 0.7 V versus RHE, with the highest value reaching 96.8%. The physical characterization reveals that fragmentation of C60 occurs together with N/O doping, both of which could induce change in electron structure, causing the formation of *COOH intermediate and ultimately leading to the optimized activity and selectivity for CO production. This treatment route was further revealed to be applicative for other carbon materials, e.g., single-walled carbon nanotube, to promote its ECR activity and selectivity. Graphical Abstract