Bulk crystals of ZnS usually take the zinc blende structure. However, the vapor deposited one-dimensional ZnS nanostructures normally take the metastable wurtzite structure. This Letter investigates the conditions under which the formed phase can be controlled between zinc blende and wurtzite in nanomaterials synthesis. The formation of pure zinc blende structured ZnS nanobelts is related not only to the lower deposition temperature (680–750 °C), but also to the size of the Au catalyst particle (<50 nm). Pure wurtzite structured ZnS nanobelts are synthesized in a relatively high deposition temperature (>750 °C) disregard the size of the Au catalyst particles.