The combination of solar irradiation and Fenton reagent have been used to enhance the biodegradability (BOD5/COD) of chlorophenol wastewater, including 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), and 2,4-dichlorophenol (2,4-DCP). Results showed that the solar photo-Fenton process improved significantly the biodegradability of chlorophenol wastewater. Basically, increasing initial H2O2 dosage was much more beneficial for increasing biodegradability of wastewater than increasing initial Fe2 +  dosage. Among the conditions studied, the optimum condition of increasing biodegradability of chlorophenol wastewater was found with a [H2O2]0/[Fe2 + ]0/[chlorophenol]0 ratio of 10.0/0.2/1.0, 10.0/0.3/1.0, and 10.0/0.2/1.0 for 2-CP, 4-CP, and 2,4-DCP, respectively. As a result, the value of BOD5/COD was increased from 0 for untreated solution up to 0.231, 0.248, and 0.193 for 2-CP, 4-CP, and 2,4-DCP, respectively with a 15-min treatment. Under the operation of optimum conditions, the oxidative state of chlorophenol wastewater could be easily controlled into a higher biodegradability stage. The COD and TOC degradation efficiency could be in excess of 90% on the whole as the preoxidized chlorophenol solution was treated by a following batch-type biological unit. In the meanwhile, the microtoxicity of wastewater reduced more than 95%.