9LiFePO4·Li3V2(PO4)3/C composite cathode material is prepared by a sol–gel method, using ferric citrate, V2O5, Li2CO3, NH4H2PO4 and citric acid as raw materials. The composite material is composed of the olivine LiFePO4 and monoclinic Li3V2(PO4)3 phases. XRD results indicate that most of the iron and vanadium in the raw materials tend to form the LiFePO4 and Li3V2(PO4)3 phases, and only small amounts of Fe and V as the dopants enter into the lattice of Li3V2(PO4)3 and LiFePO4, respectively. The electronic conductivity and Li+ diffusion coefficient of 9LiFePO4·Li3V2(PO4)3/C are 6.615×10−3 Scm−1 and ∼10−10 cm2 s−1, which are three orders of magnitude and one order of magnitude larger than those of the LiFePO4/C, respectively. The composite material shows a first discharge specific capacity of 131.3mAhg−1 and capacity retention of 95.1% after 200 cycles at 10C rate. Compared with the LiFePO4/C, its rate capability and cycle performance are both remarkably improved.