This study investigated the encapsulation and photocatalysis of chlorophenol compounds in water using porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer. The chloride ions generated during photocatalytic process were identified and quantified. 2,4,6-Trichlorophenol, pentachlorophenol, and 2,4-dichlorophenol were satisfactorily decomposed in the photoreactor using porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer, with removal efficiencies of 2,454, 498, and 760 mg/ g of porphyrin-(polystyrene-b-2-dimethylaminoethyl acrylate) star polymer. The half-life times reached around 30 min, with the exception of that for 2,4-dichlorophenol. The star polymer-impregnated porphyrin is a promising photocatalyst for the removal of chlorophenols.