The successful synthesis of ZnS hollow microspheres by a solvothermal route is reported. The synthesis was achieved by a proper selection of a sulfur source, i.e., Na2S2O3⋅5H2O or (NH2)2CS, to react with Zn(CH3COO)2⋅2H2O in mixed solvents of ethylene glycol and deionized water. The ZnS products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and photoluminescence spectroscopy. XRD identified the ZnS products to have either zinc blende or wurtzite structure. SEM images revealed hollow ZnS microspheres with 1 to 2 μm diameters and 100 to 200 nm shell thicknesses. TEM images confirmed that the hollow ZnS microspheres were assembled by ZnS crystalline nanocrystallites. The room-temperature photoluminescence spectrum of the zinc blende hollow microspheres showed a strong green emission at 514 nm and weak emission at 379 nm.