9LiFePO(4)center dot Li3V2(PO4)(3)/C is synthesized via a carbon thermal reaction using petroleum coke as both reduction agent and carbon source. The as-prepared material is not a simple mixture of LiFePO4 (LFP) and Li3V2(PO4)(3) (LVP), but a composite possessing two phases: one is V-doped LFP and the other is Fe-doped LVP. The typical structure enhances the electrical conductivity of the composite and improves the electrochemical performances. The first discharge capacity of 9LFP.LVP/C in 18650 type cells is 168 mAh g(-1) at 1 C (1 C-9LFP.LVP/C = 166 mA g(-1)), and exhibits high reversible discharge capacity of 125 mAh g(-1) at 10 C even after 150 cycles. At the temperature of -20 degrees C, the reversible capacity of 9LFP.LVP/C can maintain 75% of that at room temperature. (c) 2010 Elsevier B.V. All rights reserved.