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Electrochemical advanced oxidation process (EAOP) is known for its efficient and fast degradation of organic pollutants in polluted water treatment. In this study, the EAOP using a boron-doped diamond (BDD) anode was applied to treat two-season groundwater samples collected from four sampling wells (GS1 to GS4) with petrochemical contaminants including methyl tert-butyl ether (MTBE), benzene, toluene, chlorobenzene, total organic compounds (TOC), and total petroleum hydrocarbons (TPH) at a gas station in southern Taiwan. Moreover, toxicity tests (ATP, p53, and NF-κB bioassays) were performed to evaluate the biological responses of raw and EAOP-treated groundwater. Results show that the concentrations of chlorobenzene before and after EAOP treatment were all below its method detection limit. High degradation efficiencies were observed for MTBE (100%), benzene (100%), toluene (100%, except that of GS2 in the first season), TPH (94-97%, except that of GS4 in the first season), and TOC (85-99%). Cell viability for both the raw groundwater (81.2 ± 13.5%) and EAOP-treated samples (84.7 ± 11.7%) as detected using the ATP bioassay showed no significant difference (p = 0.715). A mean reduction in the DNA damage (739 to 165 ng DOX-equivalency L -1 (ng DOX-EQ. L -1 )) and inflammatory response levels (460 to 157 ng TNFα-equivalency L -1 (ng TNFα-EQ. L -1 )) were observed for EAOP-treated samples subjected to p53 and NF-κB bioassays. Overall, the significances of the average degradation efficiency, DNA damage, and inflammatory response before and after groundwater with EAOP treatment was observed to be significant (p < 0.05). p53 and NF-κB bioassays might be applied to assess ecotoxic risk in the environment.