A microporous selective adsorbent of carbon dioxide was constructed with raw materials such as zinc nitrate, 5-chloroisophthalic acid, and 4,4"-bipyridine, using pore size matching and chlorine functionalization strategies. The stability of the material was investigated by XRD and TG, and the results showed that it has excellent moisture stability and good thermal stability. The XPS and FTIR analysis results showed that the surface of material contains C, N, O, Cl, and Zn, and it has characteristic peaks of the functional groups of organic ligand. The analysis of specific surface area and pore size indicated that the synthesized material has a ultra microporous structure, with a most probable pore size of 0.349 nm and a BET specific surface area of 254.29 m2·g-1. Under the synergistic effect of micro pores and functionalized chlorine groups, the adsorbent exhibits good affinity for CO2. At 298 K and 100 kPa, the adsorption selectivity of CO2/C2H2, CO2/CH4, CO2/CO, and CO2/N2 were 2.80, 17.77, 34.80, and 71.47, respectively. The microporous adsorbent has moderate adsorption heat for CO2, making it easy to activate and regenerate, and its stability and reusability are excellent. So it is a good selective adsorption material for CO2.