Via a simple glycine-assisted hydrothermal route, large-scale 3D hierarchical Zn-3(OH)(2)V2O7 center dot 2H(2)O microspheres have been fabricated. Their purity, crystalline phase, morphologies and thermal stability were characterized by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), Fourier transform IR (FTIR), scanning electron microscopy (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The SEM results indicate that the microspheres are self-assembled by numerous nanoflakes with mean thickness of 100 nm. Some factors influencing the morphologies of the Zn-3(OH)(2)V2O7 center dot 2H(2)O micro-/nanostructures have been systematically investigated, as well as quantity of glycine and the reaction time. The possible mechanism of the crystal growth and assembled procedure were also proposed. The as-prepared Zn-3(OH)(2)V2O7 center dot 2H(2)O can be transformed into Zn-3(VO4)(2) with the similar morphologies by calcination in air at 600 degrees C. Furthermore, the photoluminescent properties of both Zn-3(OH)(2)V2O7 center dot 2H(2)O and Zn-3(VO4)(2) were studied and exhibited different spectra. (C) 2011 Elsevier Ltd. All rights reserved.