Li2FeSiO4/C composites doped by vanadium at Fe/Si sites have been investigated as cathode materials for lithium ion batteries. Effects of vanadium substitution at different sites on the structure of Li2FeSiO4/C are examined by X-ray diffraction, X-photoelectron spectroscopy and scanning electron microscopy. XPS results show that the oxidation state of vanadium doped at Fe sites is +3, whereas is +5 when doped at Si sites. Electrochemical measurements show that the Li2FeSi0.9V0.1O4/C sample exhibits the best electrochemical performance with initial discharge capacity of 159mAhg−1 and excellent cyclability with capacity of 145mAhg−1 at 30th cycle, which can be ascribed to larger cell volume and higher lithium ion diffusion coefficient, however, the initial discharge of the Li2Fe0.9V0.1SiO4/C sample is only 90% of the undoped Li2FeSiO4, which can be attributed to the loss of Fe content.