In present study, hollow ZnO microspheres with interior diameter of about 10 mu m were synthesized by a facile solution method using PMMA microspheres as template. The hollow microspheres are built by layers of nanoparticles with high crystallinity. The shell thicknesses are found to be about 100 nm. Based on the experimental results of XRD, SEM, TEM and XPS measurements, a possible formation mechanism for the hollow ZnO microspheres was discussed. As-synthesized hollow ZnO microspheres exhibit novel absorption band in the region of ultraviolet. Band gap of the hollow ZnO microsphere was calculated to be 3.53 based on its UV-visible absorption spectrum. (C) 2010 Elsevier B.V. All rights reserved.