The present study aims to introduce a new catalytic system, namely poly[(2-acrylamido-2-methyl-1-propane sulfonic acid-co-acrylonitrile)-Mn(III) meso tetra(N-methyl-4-pyridyl) porphine briefly called p(NaAMPS-co-AN)‐[Mn(TMPyP)]. Free-radical polymerization at ambient temperature was employed to construct this catalytic system. To prepare this heterogeneous bi-phasic catalyst, poly(NaAMPS-co-AN) was axially grafted onto the metal centers of the MnIII composite. In order to identify the amounts of metals in prepared compound, atomic absorption spectroscopy (AAS) was utilized. The results indicated that p(NaAMPS-co-AN)‐[Mn(TMPyP)] had the potential to efficiently catalyze alcohol oxidation with high selectivity in the solid-liquid biphasic reaction system. Furthermore, the catalytic activities of alcohol oxidation by the reaction-controlled phase transfer catalyst system were compared in the presence of H2O2 and TBHP, as oxidants, in a biphasic environment. It was found that functioning as a nanoreactor, the prepared catalyst system facilitated the oxidation of alcohols in water, leading to the substantial acceleration of catalytic reaction rates. After the completion of the catalytic activity, the catalyst could be separated easily from the reaction media and reused without any activity loss. In effect, the quality of the catalyst remained the same for eight cycles. The excellent performance of p(NaAMPS-co-AN)‐[Mn(TMPyP] is mostly attributed to its macroporous structure which allow for a rapid diffusion of the reactants to the reactive Mn(III) centers. High stability and reusability of catalyst without leaching is may be due to the AN. In fact, p(NaAMPS-co-AN)‐[Mn(TMPyP)] has chemical cross-linker, MBA, and physical cross-linker, AN. In a similar vein, the FT-IR spectra and atomic absorption spectroscopy confirmed the great recyclability, durability, and leaching resistance of the catalyst.