Nanostructure ZnO hollow microspheres with average crystallite size of about 15 nm, and average diameters of about 1 mu m, were successfully fabricated through a novel hydrothermal method. Hollow microspheres were formed due to self-assembly of ZnO oblong nanoparticles, which resulted in formation of a protrusive surface nanostructure. The obtained material was characterized with X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and photoluminescence (PL) investigations. The photoluminescence characterization of the nanostructure microspheres exhibited a UV irradiation at around 380 nm and a broad visible emission band centered at green region. (C) 2008 Elsevier B.V. All rights reserved.