AbstractNovel and stable films were easily assembled at the water–chloroform interface by noncovalent interaction between meso‐tetrakis(4‐sulfonatophenyl)porphyrins (H2TPPS, FeTPPS, and ZnTPPS) and polypeptide‐containing hyperbranched copolymers of various molecular weights. These films could be used as recyclable heterogeneous photocatalysts for the oxidation of 1,5‐dihydroxynaphthalene. Conversion yields of 91 and 88 % were obtained for H2TPPS and FeTPPS, respectively, and these values were much higher than those obtained for the corresponding porphyrin systems without polymers. These films could be easily utilized over 10 catalytic runs with only a slight decrease in the catalytic activity and low porphyrin loss. No separation or purification of either the catalyst or product was necessary, which proved that these porphyrin–hyperbranched copolymer films could be efficient, robust, and recyclable photooxidation catalysts.