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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.