The morphological variation of ZnO hollow miscrospheres was achieved via a two-step chemical colloidal process. The products were investigated by scanning electron microscopy, high-resolution transmission electron microscopy. Raman scattering spectroscopy, and photoluminescence spectroscopy. A possible evolution mechanism of the ZnO hollow microspheres was discussed. The lattice distortion of ZnO hollow microspheres was found on the edge of the surface. Raman spectra reveal that the E-2(high) mode of ZnO hollow microspheres is observed at 432 cm(-1). A Raman shift of 5 cm(-1) had taken place compared with the original form of the ZnO microsphere. This study helps us to understand further the structural properties of ZnO hollow microspheres synthesized by a chemical colloidal process.