H3PW12O40/ZrO2-WO3 was prepared by impregnation, and it was sensitized by H2O2 solution, its catalytic activity under simulated natural light was improved significantly. Degradation of methyl orange was used as a probe reaction to explore the influencing factors of the photodegradation reaction. The optimum conditions is that initial concentration of methyl orange is 5 mg/L, and the pH is 2.5, catalyst dosage is 0.3 g, the degradation ratio of methyl orange is as high as 91.16% after 2 h simulated natural light irradiation. The reaction of photocatalysis for methyl orange can be expressed as first-order kinetic model. The photodegradation of methyl orange, rhodamine B, basic fuchsin and methylene blue were also tested, and the degradation rate of dyes can reach 70%-91.16%.