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As Fenton reagents, Fe-based amorphous alloys have achieved good results in the treatment of dye wastewater. However, it is rarely reported how to exert the high activity and high adsorption capacity of those amorphous alloys to treat the oily wastewater with more complex components. In this article, Fe78Si8B14 amorphous ribbon was used as the anode and graphite as the cathode to degrade a kind of emulsified oil wastewater by the electro-Fenton (EF) method. The catalytic degradation under such processing parameters as current density, pH values, and H2O2 concentration was investigated. The catalytic performance of the Fe-Si-B amorphous ribbon was characterized by using the degradation efficiency of the emulsified oil wastewater. The water samples before and after degradation by Fe-Si-B amorphous ribbons were examined by infrared spectrophotometry and gas chromatography-mass spectrometer (GC-MS), respectively. The results show that the degradation efficiency of 99.91% is obtained under optimum process conditions of the current density of 30 mA/cm2, pH value of 3, and H2O2 concentration of 20 g/L. Furthermore, all the long-chain organic compounds in the emulsified oil wastewater are decomposed into short-chain organic substances within 40 min of the reaction. Therefore, the EF method with amorphous alloy as anode and graphite as cathode has a good prospect for the degradation of emulsified oil wastewater. Moreover, the obtained results provide a theoretical basis and guidance for the application of amorphous alloy catalysts in practical wastewater remediation applications. [ABSTRACT FROM AUTHOR]