The anionic manganese (III) porphyrin was immobilized onto crosslinked poly(benzylpicoline-co-styrene) resin through coordinate linkage. The immobilized metalloporphyrin was employed as a heterogeneous catalyst for the hydroxylation of cycle-octane by NaOCl. The observed reaction rates depend on experimental parameters such as stirring speed, substrate amount, temperature, and catalyst amount. The influence of different polymer-based axial ligands, particle size, and percent crosslinking of the polymer support was also discussed. The imidazole-based polymer supports show higher rate constant values than the pyridine-based supports. The catalyst shows significant decrease in catalytic activity on recycling.