The intrinsically low electronic conductivity of Li3V2(PO4)(3) (LVP) is a major drawback to be widely used as cathode materials for Li-ion battery. In this study, we synthesized novel LVP composites combining them with carbon nanofiber (CNF) and graphene with improved electrochemical performance. The specific capacity of LVP/CNF-graphene (LVP-CG) was 207 mAh g(-1) at 0.1C between 3.0 and 4.8 V, which is beyond the theoretical capacity of LVP (197 mAh g(-1)). Moreover, the LVP-CG composite shows smaller particle size, high surface area, improved electronic kinetic behavior and low resistance in the LVP electrode. Our results demonstrate that novel composite with CNF and graphene can be widely used in other phosphate-based cathode materials for advanced Li-ion batteries. (C) 2015 Elsevier Ltd. All rights reserved.