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The contamination of antibiotics in aqueous environment causes increasing concerns recently. Light-assisted activation of peroxydisulfate (PDS) has been demonstrated as an efficient technology for removal of contamination in water. Herein, a hollow sphere of CuWO4 (h-CuWO4) was employed as a visible light-activated photocatalyst for the activation of PDS, and following with high removal efficiency (98％) of antibiotic sulfamethoxazole (SMX). Under visible light irradiation, the degradation rate on hollow structures system is nearly 2 times higher than the traditional solid CuWO4 spheres. Furthermore, the underlying mechanism and detailed pathway of SMX degradation were proposed based on density functional theory (DFT) calculations and liquid chromatography-mass spectrometry (LC–MS). This work provides a new feasible way for advanced oxidation processes to remove antibiotics SMX in heterogeneous system, and open up new application possibilities of CuWO4-based materials.