9LiFePO4·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 168mAhg−1 at 1C (1C9LFP·LVP/C =166mAg−1), and exhibits high reversible discharge capacity of 125mAhg−1 at 10C even after 150 cycles. At the temperature of −20°C, the reversible capacity of 9LFP·LVP/C can maintain 75% of that at room temperature.