The materials composed of Li3V2(PO4)(3)/C nanoparticles and multi-walled carbon nanotubes (MWCNTs) with continuous three-dimensional (3D) network are synthesized using a rapid microwave assisted hydrothermal route. The MWCNTs-decorated Li3V2(PO4)(3)/C nanocomposite is characterized and studied in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and various electrochemical measurements. The electrode fabricated from this nanocomposite shows effective electron and ion transport. When the materials used as cathode material for lithium-ion batteries, it exhibits a high reversible capacity and superior cycle stability which is attributed to the chemical interaction between the Li3V2(PO4)(3)/C nanoparticles and the functional groups on the surface of MWCNTs evidenced by the SEM, TEM, XPS and Raman spectroscopy results. This design conception and synthesis strategy presented here offer a simple and rapid method to obtain high performance Li3V2(PO4)(3) cathode material for high-rate and long-life rechargeable lithium-ion batteries. (C) 2015 Elsevier Ltd. All rights reserved.