In this paper, microsaws and microtowers have been prepared by vapor–liquid–solid (VLS) and vapor–solid (VS) methods, respectively, which are based on thermal evaporation. The role of Au catalyst in defining the morphology of the ZnS microstructures has been found. The microsaws were synthesized onto the sapphire substrate in the presence of Au catalyst, and the microtowers were produced onto Au-uncoated sapphire substrate. The microstructural changes were studied through a scanning electron microscope. The structural characterization of the microstructures was indicated by X-ray diffraction and a high-resolution transmission electron microscope. Room temperature photoluminescence measurements with 325nm excitation showed four emission bands located at ∼400nm, ∼480nm, ∼520nm and ∼580nm.