Large-scale novel hierarchical ZnO microspheres were fabricated by a facile precursor procedure in the absence of self-assembled templates, organic additives, or matrices. A field emission scanning electron microscopy (FESEM) image reveals that the ZnO microspheres with diameter of 5-18 mu m are built by sheet-like ZnO networks with average thickness of 40 mu m and length of several microns. High resolution transmission electron microscopy (HRTEM) image indicates that the building blocks, sheet-like ZnO networks, are porous mesocrystal terminated with {01 - 10} crystal planes. A potential application of the ZnO microspheres as a catalyst in the synthesis of 5-substituted 1H-tetrazoles was investigated. It was found that the hierarchical ZnO microsphere catalyst exhibits structure-induced enhancement of catalytic performance and a strong durability. (C) 2012 Elsevier BM. All rights reserved.