A facile approach is reported for the preparation of hollow ZnO microspheres using Zn powders as raw materials. Firstly, Zn(OH)(2) was precipitated on the surface of Zn powder to form core/shell structure in solution, and subsequent calcination these core/shell composite particles at 650 degrees C in air would lead to the formation of ZnO hollow spheres whose diameter were determined by the dimension of the used Zn powder. XRD, TEM, SAED, EDS and UV-vis were used to characterize the as-prepared samples. A formation mechanism is proposed to be a process following the formation of Zn/Zn(OH)(2) core/shell particles, the decomposition of Zn(OH)(2) shell to ZnO, and the sublimation and oxidation of Zn core. (c) 2005 Elsevier B.V. All rights reserved.