Large-scale well-aligned rod-like and flower-like YVO4:Eu3+ crystals were prepared on glass substrates by a hydrothermal method in a controllable way with additive ethylenediamine tetraacetic acid disodium salt [Na2H2L center dot 2H(2)O]. No extra surfactants or templates were used. In the synthesis process, well-aligned YVO4:Eu3+ microrods were fabricated on YVO4: Eu3+-seed-coated substrates. The YVO4:Eu3+ seed precursor was prepared by a sol-gel reaction. And well-defined flower-like YVO4:Eu3+ microstructures were fabricated on bare substrates. The products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and photoluminescence (PL). TEM and SEM studies reveal that the flower-like superstructure is composed of dozens of radially oriented rhombus-shaped microrods and the crystalline microrods with rectangle cross-sections and well-defined crystallographic faces are grown directly onto the substrates. This convenient method may be applicable to prepare other orthovanadate phosphors with 3D morphologies. (C) 2008 Elsevier B.V. All rights reserved.