Abstract: Sulfonated poly(ether ether ketone)-poly (vinyl alcohol)(SPEEK-PVA) macromolecular compound system was prepared by blending method. It can produce macromolecular active radicals under UV irradiation which were used for degrading of simulated pollutant methyl orange. The properties and photodegrading mechanism of SPEEK-PVA compound for methyl orange in the solution was discussed. The influence of sulfonated degree of SPEEK, SPEEK-PVA quality ratio, crosslinking agent, pH and O2 on dye degradation effects were investigated. The optimal processes of the SPEEK-PVA compound were as follows, sulfonated degree of SPEEK was 73.3%, crosslinking agent mass fraction was 6%, pH was 2.3, mass ratio of SPEEK to PVA was 1/3. Under this condition, the degradation rate of 10 mg/L methyl orange dye reached 87.8% after 1 h. The macromolecular radicals generated from the system under the condition of light can stimulate the O2 to form active oxygen free radicals, which could greatly increase the degradation rate.