In this study, using bentonite-supported Fe(II)/phosphotungstic acid composite (HPW-Fe-Organicbent) prepared by mechanochemical synthesis as heterogeneous catalyst, the photo-Fenton degradation of ethyl xanthate under visible light irradiation was studied in detail. The results showed that the degradation of ethyl xanthate was mainly impacted by H2O2 dosage, catalyst dosage and reaction time. HPW-Fe-Organicbent catalyst had a wide applicable range of pH and kept a high catalytic activity even at high pH in the photo-Fenton degradation of ethyl xanthate. It was found that the degradation of ethyl xanthate in the photo-Fenton process catalyzed by HPW-Fe-Organicbent mainly resulted from the hydroxyl radicals. HPW-Fe-Organicbent had an excellent stability in use, and retained almost all of its catalytic activity for four recycling times. Moreover, the kinetics study showed the degradation of ethyl xanthate, with the initial concentration below 50 mg/L, was well fitted by the pseudo-first-order rate model.