Nanocrystalline Li3V2(PO4)(3)/C composite synthesized using a novel corn assisted combustion method at 850 degrees C exhibits superior physical and electrochemical properties than the one synthesized at 800 degrees C. Despite the charge disproportionation of V4+ and a possible solid solution behavior of Li3V2(PO4)(3) cathode upon insertion and extraction of Li+ ions, the structural stability of the same is appreciable, even with the extraction of third lithium at 4.6 V. An appreciable specific capacity of 174 mAh g(-1) and better capacity retention upon high rate applications have been exhibited by Li3V2(PO4)(3)/C cathode, thus demonstrating the suitability of the same for lithium-ion battery applications. (C) 2012 Elsevier Ltd. All rights reserved.