Formation of solid solutions is a good strategy to acquire materials with special properties and bring forth new type of applications or enhance the performance of currently existing devices. In this study, hollow ZnxCd1-xS nanospheres with different molar ratios were synthesized via a facile hydrothermal process. The products were fully characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and UV-vis absorption spectroscopy. It was found that the photocatalysis performance of the as-prepared samples could be enhanced by formation of ZnxCd1-xS solid solutions. In addition, their photocatalytic activities are dependent on the Zn/Cd molar ratios and nanostructures of ZnxCd1-xS solid solutions. Hollow Zn0.2Cd0.8S spheres exhibit extremely high photocatalytic activity and good re-usability, and the photocatalytic conversion of RhB reaches as high as 96% after 50 min of irradiation.