A simple method of vapor deposition for the shape selective synthesis of ZnO structures, namely, multipods, submicron wires, and spheres, has been successfully demonstrated. A plausible growth mechanism based on the studies of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) is proposed. Our studies suggest that the growth of a multipod structure is governed by the screw dislocation propagation while the vapor−liquid−solid (VLS) mechanism is responsible for the formation of submicron wires and spheres. Moreover, the flow rate of the carrier gas plays a crucial role in governing the morphology. Further, these structures exhibit an enhanced field emission behavior. The nonlinearity in the Fowler−Nordheim (F−N) plot, a characteristic feature of electron emission from semiconductors, is explained by considering the contributions from both the conduction and the valence bands of ZnO.