The hexagonal phase wurtzite-type ZnS microspheres are synthesized by the hydrothermal method at relatively low reaction temperature (160 ℃), with glutathione (GSH) as the sulfur source, ZnCl2 as the zinc source, hexadecyl trimethylammonium bromide (CTAB) as the surfactant, and ethylenediamine as the reaction medium. The morphologies of microspheres are observed by scanning electron microscope, and their phase structures are analyzed by X-ray diffraction. In addition, the optical properties of samples synthesized under different conditions are characterized by fluorescence spectrometer and ultraviolet spectrophotometer. The experimental results show that CTAB can promote the formation of hollow spheres. The monodispersed hexagonal phase wurtzite-type ZnS microspheres at micrometer scale, which are composed of nanoparticles, can be obtained at relatively low reaction temperature when CTAB is used as the porogens. The ZnS hollow microspheres with different shell thicknesses can be synthesized by changing the reaction parameters. The test results show that the fluorescence intensity of hollow microspheres is higher than that of solid microspheres.