Oilfield produced water was treated by photocatalysis, electro-oxidation, and photoelectrocatalysis, respectively. The chemical composition and toxicity of the raw effluent and treated products were assessed by chemical and mutagenicity analysis. The raw effluent exhibited mutagenic activity in both strains of Salmonella typhimurium. The lowest concentration of the dichloromethane extract capable of inducing a positive response in strains TA98 and TA100 were as low as 4 and 5 microg/plate, respectively. All three technologies could detoxify direct-acting mutagenic organic pollutants efficiently, although they could not completely eliminate mutagenicity in the water after 60 min of treatment. At equivalent doses, photoelectrocatalysis exhibited the greatest capability to reduce genotoxicity, whereas photocatalysis was the least effective and did not cause appreciable change in mutagenicity. The gas chromatography-mass spectrometry (GC-MS) analysis revealed that n-alkanes (259.4 ng/L) and phenolic compounds (2,501.4 ng/L) were the main organic constituents in the oilfield produced water. Thus, the results of both biological and chemical analysis indicate that photoelectocatalysis was the most effective technology for degradation of oilfield wastewater.