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The greenhouse gas (GHG) emissions from fossil fuel combustion and carbon dioxide (CO2) cause global warming and climate change. In this study, we synthesized three porphyrin-based azo-porous organic polymers (PBPOP1, PBPOP2, and PBPOP3) that enable the capture and one-step conversion of CO2. These catalysts effectively capture the CO2molecules over N2in a post-combustion environment. PBPOP3 exhibited an enhanced CO2/N2selectivity at 313 K, with a value of 534. We characterized the porphyrin-based azo-POPs catalysts using FT-IR, 13C solid-state NMR, XRD, TGA, and HR-FESEM. We evaluated the gas adsorption properties using Brunauer–Emmett–Teller analysis, which included adsorption–desorption isotherms, NLDFT pore-size distribution, and adsorption at 298, 313, and 353 K. The fixation of CO2with styrene oxide and phenyl glycidyl ether was performed using catalysts for conversion to styrene carbonate (tetra-n-butylammonium bromide was used as a co-catalyst). Thus, our findings can be used for reducing the amount of CO2gas in the atmosphere by synthesizing porphyrin-based azo-POP catalysts.