ZnO microwires with hexagonal, dodecagonal, and circular cross sections were achieved by a micro-environment control vapor deposition method. Laser induced micro-photoluminescence spectra of single wires showed separated emission modes in the visible range, and in which the higher the number of sides in cross section for the ZnO MWs, the more resonant modes are induced. Theoretical calculations indicated the nature of resonant whispering-gallery modes, in agreement with the spectral and mapping profiles of these modes. The results demonstrated that the as-prepared ZnO MWs can be used as high-quality microresonators to produce whispering-gallery modes.