The feasibility study of the application of the photoelectrocatalytic decontamination of high saline produced water containing refractory organic pollutants was investigated in the slurry photoelectrocatalytic reactor with nanometer TiO2 particle prepared with sol-gel method using the acetic acid as hydrolytic catalyst. The efficiency of the photoelectrocatalytic decontamination of produced water was determined with both COD removal from the tested wastewater and the decrease of mutagenic activity evaluated by Ames tests. The experimental results showed that the photoelectrocatalysis is a quite efficient process for decontaminating the produced water, although there are high concentration of salt existed in oilfield wastewater. We found that the COD removal efficiencies by photoelectrocatalytic process are much higher than that of by photocatalytic or electrochemical oxidation individually in the photoelectrocatalytic reactor. The COD removal can be substantially improved by the added H2O2 and the generation of active chlorine from high concentration chlorides in the wastewater. The effects of various operating conditions, such as initial COD concentration, applied cell voltage, catalyst amount and initial pH value of solution, on the photoelectrocatalytic efficiencies, is also investigated in detail. The results showed that when the raw produced wastewater was diluted in a 1:1 (v/v) ratio, there is a highest COD removal efficiency. And the photoelectrocatalytic degradation of organic pollutants in saline water is much favored in acidic solution than that in neutral and/or alkaline solution.