The photochemical degradation of 4-chlorophenol (4-CP) using ultraviolet irradiation (UV) of 6, 12 and 18 W with peroxyacetic acid (PAA) was studied in a batch reactor. The objective of this work was to investigate degradation and mineralization of 4-CP by PAA. The degradation efficiency increased with increasing UV input. The degradation process was also pH and initial PAA concentration dependent. The optimum conditions for the photochemical degradation of 4-CP as UV input, pH and PAA concentration was found to be 18 W, 9.5 and 3,040 ppm. The reaction efficiency decreased with increasing initial 4-CP concentrations. More than 95% mineralization of 4-CP was achieved with the UV/PAA process. The chloride ion concentration and chemical oxygen demand (COD) was evaluated. The chloride ion concentration and COD were decreased gradually with increasing UV input. Samples were analyzed by high pressure liquid chromatography (HPLC), UV spectrophotometry and gas chromatography–mass spectrometry (GC-MS) for residual concentration and identification of final degraded products.