Highly active photocatalyst, having certain anti-ionic interfering function, of F, S and Bi doped TiO2/SiO2 was used for the first time to degrade the organic pollutants in acrylonitrile industrial wastewater under natural sunlight. The photocatalyst were prepared and characterized by UV-Vis, XRD, TEM, EDS, Nitrogen physical adsorption and XPS technique. UV-Vis analysis revealed addition of F, S and Bi into the lattice of TiO2 led to the expansion of TiO2 response in the visible region and hence the efficient separation of charge carrier. The photocatalytic potential of as prepared catalyst to degrade acrylonitrile wastewater under simulated and natural sunlight irradiation was investigated. The extent of degradation of acrylonitrile wastewater was evaluated by chemical oxygen demand (CODCr). CODCr in wastewater decreased from 88.36 to 7.20 mgL-1 via 14 h irradiation of simulated sunlight and achieved regulation discharge by 6 h under natural sunlight, illuminating our photocatalyst effectiveness for refractory industrial wastewater treatment. From TEM results, we found that SiO2 could disperse the photocatalyst with different component distributions between the surface and the bulk phase that should also be responsible for the light absorption and excellent photocatalytic performance. The XPS analysis confirmed the presence of surface hydroxyl group, oxygen vacancies.