The synergetic effect of nitrogen-rich and CO2-philic filler and polymer in mixed matrix-based membranes (MMMs) can separate CO2 competently. The introduction of well-defined nanostructured porous fillers of pores close to the kinetic diameter of the gas molecule and polymer matrix compatibility is a challenge in improving the gas transportation characteristics of MMMs. This study deals with the preparation of porphyrin filler and the polysulfone (PSf) polymer MMMs. The fillers demonstrated uniform distribution, uniformity, and successful bond formation. MMMs demonstrated high thermal stability with a glass transition temperature in the range of 480�610 °C. The porphyrin filler exhibited microporous nature with the presence of �-� bonds and Lewis's basic functionalities between filler-polymer resulted in a highly CO2-philic structure. The pure and mixed gas permeabilities and selectivity were successfully improved and surpass the Robeson's upper bound curve's tradeoff. Additionally, the temperature influence on CO2 permeability revealed lower activation energies at higher temperatures leading to the gas transport facilitation. This can be granted consistency and long-term durability in polymer chains. These results highlight the unique properties of porphyrin fillers in CO2 separation mixed matrix membranes and offer new knowledge to increase comprehension of PSf performance under various contents or environments. © 2021 Elsevier B.V.