Nanostructures of tetragonal PrVO4 with novel 3D hierarchical architectures self-assembled nanorods were successfully synthesized by a hydrothermal method in ethylenediamine tetra-acetic acid (EDTA) mediated processes. Comprehensive structural, morphological studies like X-ray diffraction, scanning and transmission electron microscopy were employed to characterize the as-obtained products. In the hydrothermal process, EDTA not only acts as a chelating reagent to facilitate the formation of PrVO4, but also acts as a surface capping agent to adhere to the newly created surface and to promote the crystal splitting. The formation mechanisms of nanorods to hierarchical architectures were proposed on the basis of a series of surfactant and time-dependent experiments. Photoluminescence (PL) studies of PrVO4 showed strong red emission upon UV illumination, and this implied potential application in the luminescent field. A possible growth mechanism of the sheaf-like PrVO4 hierarchical nanocrystals is proposed and discussed. (C) 2011 Elsevier B.V. All rights reserved.