The controlled synthesis of Zn-3(OH)(2)V2O7.nH(2)O hierarchical structures has been successfully realized in a large scale via a simple hydrothermal method. It was demonstrated that the morphologies of the final products are significantly affected by the quantity of hexamethylenetetramine, reaction temperature and reaction time. Optimum amount of sodium sulfate plays a crucial role in the development of crystallinity of the products. The morphology evolvement and the growth mechanism were discussed, and sulfate induced oriented attachment and temperature facilitated Ostwald ripening process were proposed for the possible formation mechanism. The structure and morphology of those products were characterized by X-ray diffraction (XRD), Raman spectrum, field-emission scanning electron microscopy (FE-SEM) equipped with energy dispersion spectrum (EDS). Furthermore, the photoluminescence properties of those products were researched. Excellent visible light emission ranging from 400 to 700 nm was exhibited via room temperature photoluminescence (PL) measurement. (C) 2009 Elsevier B.V. All rights reserved.