LiFe0.9V0.1(PO4)(0.95)F-0.15/C was prepared via solid-state carbothermal reaction (CTR). F and V codoping did not alter the olivine structure of LiFePO4 but reduced the particle size and improved the Li+ diffusion coefficient. The cells based on this material showed higher discharge capacity, working voltage, rate capability, and better cyclic performance than that of undoped and F-doped materials.