The size- and morphology-controlled growth of ZnO nanowire (NW) arrays is potentially of interest for the design of advanced catalysts and nanodevices. By adjusting the reaction temperature, shelled structures of ZnO made of bunched ZnO NW arrays are prepared, grown out of metallic Zn microspheres through a wet-chemical route in a closed Teflon reactor. In this process, ZnO NWs are nucleated and subsequently grown into NWs on the surfaces of the microspheres as well as in strong alkali solution under the condition of the pre-existence of zincate (ZnO22–) ions. At a higher temperature (200 °C), three different types of bunched ZnO NW or sub-micrometer rodlike (SMR) aggregates are observed. At room temperature, however, the bunched ZnO NW arrays are found only to occur on the Zn microsphere surface, while double-pyramid-shaped or rhombus-shaped ZnO particles are formed in solution. The ZnO NWs exhibit an ultrathin structure with a length of ca. 500 nm and a diameter of ca. 10 nm. The phenomenon may be well understood by the temperature-dependent growth process involved in different nucleation sources. A growth mechanism has been proposed in which the degree of ZnO22–saturation in the reaction solution plays a key role in controlling the nucleation and growth of the ZnO NWs or SMRs as well as in oxidizing the metallic Zn microspheres. Based on this consideration, ultrathin ZnO NW cluster arrays on the Zn microspheres are successfully obtained. Raman spectroscopy and photoluminescence measurements of the ultrathin ZnO NW cluster arrays have also been performed.