We report the synthesis and characterization of ZnS nanostructures, which were grown by thermal evaporation of the ZnS powder at high temperature using iron network as the collection substrate. Scanning electron microscopy investigations show that the products present taper-like morphologies. Transmission electron microscopy studies indicate ZnS nanostructures are well crystallized. The formation mechanism of the novel nanostructure is discussed on the basis of the experimental results; The nanostructure is formed due to a fast growth of ZnS nanowire along  and the subsequent “epitaxial” radial growth of the ZnS nanocone along the six (01-10) surfaces around the nanowire. A strong room-temperature photoluminescence in ZnS nanostructures has been demonstrated.