In spite of recent progress in developing hollow micro/nanostructures, the synthesis of three-dimensional adsorbents with high adsorption efficiency and capability on the basis of these structures still remains a great challenge. Herein, we demonstrate a facile hydrothermal strategy to synthesize uniformly dispersed hollow CuWO4 spheres. The as-prepared CuWO4 spheres with unique mesoporous structure show favorable selective adsorption for cationic dyes and good recyclability. The adsorption capacity of hollow CuWO4 towards methylene blue (MB) reaches 59.82 mg g(-1). Furthermore, the hollow CuWO4 spheres present enhanced photoelectrochemical performance under visible light illumination. This strategy of acquiring specifically functionalized materials from smart design and simple chemical process has opened up wide opportunities on the fabrication of alternative absorbents and photoelectrodes based on CuWO4 substrate. (C) 2018 Elsevier Inc. All rights reserved.