Based on the double activation model of the epoxide, zinc phthalocyanine-based porous organic polymer (denoted as ZnPc-POP) was prepared by Schiff-base condensation reaction with zinc tetraminophthalocyanine and 1,3,5-benzenetricarboxaldehyde under solvothermal conditions. The structure was characterized by FTIR, 13CMAR NMR, XPS, TEM and nitrogen adsorption desorption. Using the cycloaddition reaction of epichlorohydrin (ECH) and CO2 as the model and tetrabutylammonium bromide (TBAB) as the cocatalyst, the catalytic performance, recycling ability and substrate applicability of ZnPc-POP were investigated, and the catalytic mechanism was also explored. The results show that ZnPc-POP has abundant mesoporous structure (pore volume is about 0.64 cm3/g, average pore size is about 20 nm) and high specific surface area (171.6 m2/g). At 100 ℃ and 1.0 MPa, the selectivity of ECH to produce cyclic carbonate was more than 99%, the yield was 96%, and the conversion frequency (TOF) was up to 533.3 h-1. ZnPc-POP can be recycled at least 5 times without significant decrease in the catalytic activity. The oxygen atom in the epoxide is activated effectively by coordination with the the Lewis acidic zinc center of ZnPc-POP, and the bromine ion in the co-catalyst TBAB promotes the ring-opening of the epoxide through nucleophilic attack. This double activation of epoxide ring-opening is the rate-controlling step of the CO2 cycloaddition reaction.