The photochemical oxidation of 4-chlorophenol solutions by ultraviolet irradiation/sodium hypochlorite (UV/NaClO) and ultraviolet irradiation/ozonation (UV/O3) respectively was studied in a pilot scale photochemical reactor. The degradation efficiency of UV/NaClO was lower than that of UV/O3. The final UV absorption removals of the two processes were approximately 80% and approximately 90% respectively. During the two processes, dihydroxylated chlorophenols were the main intermediates. And pH values decreased with the oxidation being carried on. However, the UV/NaClO process was incomplete and some adsorbable organic halogens, such as ethyl 2-chloroacetate, 3,4-dichlorobut-3-en-2-one, ethyl 2,2-dichloroacetate, 2-chloro-1,1-diethoxyethane, ethyl 2,2,2-trichloroacetate and 2,4,6-trichlorophenol, still existed in the final solution. The costs of the two processes were also estimated. On a small scale, UV/NaClO process had significant economic advantage.