The rational synthesis of earth-abundant materials with excellent electrocatalytic performances plays a critical role in electrochemical CO2 reduction (ECR) to obtain value-added chemical products or fuels. Here we demonstrate a defective graphene (DG) as such an electrocatalyst candidate via a nitrogen removal method. The graphene with a large amount of topological defects offered abundant catalytically active sites, high electronic conductivity and strong adsorption of CO2. Attributed to these features, the DG exhibited significantly higher electrocatalytic CO2 reduction performances with an excellent faradaic efficiency of 84% at 0.6 V vs. reversible hydrogen electrode and a larger current density, compared to pristine graphene, nitrogen-doped graphene and edge-rich graphene. This work suggests a promising method for further designing efficient metal-free electrocatalysts for CO2 reduction. (C) 2018 Elsevier Inc. All rights reserved.