Micrometer-sized porous honeycomb-patterned thin films based on hybrid complexes formed via electrostatic interaction between Mn(III) meso-tetra(4-sulfonatophenyl) porphine chloride (an acid form, {MnTPPS}) and dimethyldioctadecylammonium bromide (DODMABr). The morphology of the microporous thin films can be well regulated by controlling the concentration of MnTPPS-DODMA complexes, DODMABr, and polystyrene (PS), respectively. The formation of the microporous thin films was largely influenced by different solvents. The well-ordered microporous films of MnTPPS-DODMA complexes exhibit a more efficient antibacterial activity under visible light than those of hybrid complexes of nanoparticles modified with DODMABr, implying that well-ordered microporous films containing porphyrin composition can improve photochemical activity and more dominance in applications in biological medicine fields.