ZnS nanostructures with different morphologies, sizes, and microstructures were synthesized by the evaporation of ZnS nanopowders. Based on the appearance of the as-synthesized products, we show that substrate temperature and catalyst are the critical factors for controlling the size and the structure of various kinds of ZnS nanostructures, such as nanorods, nanowires, nanobelts, and nanosheets. Within a certain temperature range, products with a specific morphology can be obtained. Therefore, it may be possible to obtain ZnS nanostructures with a specific morphology by controlling the reaction temperature and catalyst. This represents an important step toward the design and control of nanostructures. High-resolution electron microscopy revealed that most of the nanorods and nanowires grew along the [100] direction, whereas most of the nanobelts and nanosheets grew along [001]. Photoluminescence properties and growth mechanisms of these as-synthesized ZnS nanostructures are discussed.