Defect structure is one of the crucial factors for enhancing the catalytic activities of photocatalysts. However, rational design and construction of defect structures in catalysts to meet the aim of enhancing photocatalytic performance in a simple and cost-effective way is still a challenge. In this contribution, we report a strategy to construct defect structures in graphitic carbon nitride (g-CN) by simple copolymerizing of urea with polyethyleneimine (PEI). Among the prepared catalysts, u-0.05PEI presents the best photocatalytic activity for CO2 reduction, with CO and CH4 yields of 32.86 and 1.68 mu mol g(-1) in 4 h, which is about 3.2 and 2.5 times higher than that of g-CN, respectively. Characterization results show that both C and N defects are formed in the newly prepared catalysts. The C defects on the surface of u-xPEI result in the formation of more amino groups which are beneficial for CO2 adsorption. Meanwhile, the N defects inside the samples lead to the generation of midgap states between the valance band and conduction band of u-xPEI. The midgap states greatly enlarge the light absorption extent, and enable the use of light with energy lower than the intrinsic absorption of g-CN in the photoreduction of CO2. As confirmed by DRS, EPR, PL analysis, the excellent catalytic activity of u-0.05PEI is mainly attributed to the remarkably improved light utilization efficiency and fast charge transfer. Moreover, the reaction is performed in water without any additive or organic solvent, which makes it environmentally friendly. (C) 2020 Elsevier Inc. All rights reserved.