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The heterogeneous and multifunctional charged polymers have broad application prospects in modern catalysis. One of the valid methods of synthesizing multifunctional charged polymers is incorporating metalloporphyrins with halide anions. Herein, a series of zinc(II)porphyrin-based porous ionic polymers [PIP-ZnTIPP/DVB (1:m) (m = 20, 40, 60, 80)] were synthesized by combining imidazolium-functionalized Zn-porphyrin (ZnTIPP) and divinylbenzene (DVB) through the free-radical copolymerization by a solvothermal method. The rigid PIPs have many physical advantages such as spatial separation of Zn-porphyrin sites, high thermal stability, hierarchical pore structures, high specific surface area, and abundant imidazolium (Br − ) group in the polymeric skeletons, which exhibit fantastic catalytic activity for the coupling reaction of epoxides and CO 2 without any solvent or cocatalyst. In particular, the catalyst PIP-ZnTIPP/DVB (1:20) displayed the highest catalytic activity with a yield of 99% and a turnover frequency (TOF) of 759 h −1 and could be recycled six times without the loss of activity. The excellent catalytic activity results from a synergistic effect between zinc sites and nucleophilic bromide anions.