Integrating reactive Lewis acid sites and nucleophilic anions into porous materials is a promising approach to develop efficient heterogeneous catalysts for the cycloaddition of CO2 to epoxides (CCE) into cyclic carbonates. In this work, ZnBr42− coordination anions consisting of Zn2+ ions as Lewis acid sites and Br− ions as nucleophiles were immobilized on the poly (styrene–divinylbenzene) anion-exchange resin D201 containing quaternary ammonium cationic groups through a simple ion-exchange method. The obtained catalyst, named ZnBr4-D201, was characterized by X-ray Photoelectron Spectroscopy (XPS), scanning electron microscopy (SEM) and thermo-gravimetry (TG). Under the condition of solvent and co-catalyst free, ZnBr4-D201 exhibited efficient catalytic activity for CCE reaction. Take the cycloaddition of CO2 to 1,2-epoxybutane (BO) as an example, ZnBr4-D201 gave a BO conversion rate of 97 % and a selectivity of 98 % for cyclic carbonate with a high TOF value at 1 MPa CO2 and 80 °C for 6 h, which is superior to most of heterogeneous catalysts ever reported. Furthermore, ZnBr4-D201 showed good recoverability, and the yield of cyclic carbonate was still up to 82 %. The excellent catalytic performance and convenient preparation process make ZnBr4-D201 have great potential for CCE reaction in practical production.