ZnO nanostructures were grown directly on sapphire substrates and GaN epilayers by thermal evaporation. Their morphologies and densities were found to be strongly dependent on the synthesis position and the kinds of substrate loaded into the reactor due to the different oxygen densities and the lattice mismatch, respectively. Scanning electron microscopy and transmission electron microscopy studies revealed that ZnO nanorods on sapphire substrates grew in four directions, one 〈0001〉Sapphire and three (1014)Sapphire directions. It was found that the in-plane lattice mismatch of inclined ZnO nanorods was remarkably reduced by forming the planar relationship of (0002)ZnO//(1014)Sapphire, compared to that of (1120)ZnO//(1010)Sapphire in the ZnO film. On the other hand, for the GaN epilayers, vertically well-aligned ZnO nanorods were grown after growing an epitaxial ZnO film due to reduced lattice mismatch. Electron energy-loss spectroscopy data showed that Zn-rich stoichiometry was responsible for the formation of ZnO nanostructures.