A class of novel poly(ionic liquid)s-ZnX₂ complexes ([IMEP]R-ZnX₂ (R = Cl, Br, X = Cl, Br, I) with multi-functional active sites were fabricated by a facile method and initially employed as efficient heterogeneous catalysts for transformation of CO₂ and epoxides into corresponding cyclic carbonates without the aid of any organic solvent and co-catalyst. Therein, the one-pot fabrication of poly(ionic liquid)s was realized using imidazole and epibromohydrin or epichlorohydrin as raw materials. The catalysts revealed pronounced activity and selectivity toward the cycloaddition reaction under the optimal conditions (120ºC, 2.0 MPa and 3 h). The effect parameters of the reaction, such as reaction temperature, duration time, initial CO₂ pressure, amount of catalyst, the counter anions and halide ions of the catalysts were also investigated. The cooperative effect of Lewis acidic Zn sites and hydroxyl group for polarizing the oxygen atom of epoxide, together with the nucleophilic attack of X^- on the adjacent β-carbon atom of epoxide promotes readily the ring-opening, thus leading to the enhanced activity. In addition, the catalytic activity can be retained substantially after five times of recycling test.