Semiconductor LaFeO₃ perovskites fabricated via the sol-gel method were used as a peroxydisulfate(PDS)activator for methylene blue(MB)degradation under visible light, and the degradation efficiency and mechanism of organic matter were evaluated. Results indicated that the complex superior oxidation system Vis/LaFeO₃/PDS exhibited promising efficiency in the degradation of MB in a wide pH range. Specifically, 92. 4% of MB with a concentration of 30 mg/L was degraded with the addition of 0. 5 g/L LaFeO₃ and 0. 5 mmol/L PDS within 30 min. The combination of the photocatalytic process with the activation performance of LaFeO₃ to PDS could restrain recombination of the photo-generated electron-hole pairs in the bulk of semiconductor, resulting in efficient redox cycles of Fe(Ⅱ)/Fe(Ⅲ)and conversion from oxygen vacancy to active oxygen, which enhanced production efficiency and oxidative activity capacity of h⁺, SO^-₄·, and ¹O₂. Therefore, Vis/LaFeO₃/PDS is an efficient combination of photocatalysis and sulfate radical-based advanced oxidation technology and makes it a promising method in the treatment of refractory organic pollutants due to its synergistic effect.