Li3VO4 was prepared by a solid-state method. Appropriate ratios of dried V 2 O 5 and Li 2 CO 3 powders (Li:V = 3:1 in mol/mol) were mixed thoroughly using an agate mortar, then the mixture were annealed at 600 °C for 5 h followed by 900 °C for 3 h in air in an temperature-controlled furnaces. The obtained powder was grounded for use as an active electrode material for battery tests. Powder X-ray diffraction (XRD) patterns were collected with a Bruker D8 Advanced Diffractometer using Cu K a radiation. The morphologies of the samples were examined by fi eld-emission scanning electron microscopy (FE-SEM, Hitachi S-4800) and high-resolution transmission electron microscopy (HRTEM, JEOL JEM-3000F). For Ex-situ XRD measurements, the electrode was picked from a freshly charge/ discharged coin-type cell and sealed with Mylar fi lm in an argon-fi lled glove box, and then immediately performed the XRD measurement. The electrochemical performances were measured with coin-type cells which coupled a Li3VO4 composite electrode and a Li metal electrode. The Li3VO4 composite electrode was made by 75% of Li3VO4 , 20% of conducting agent and 5% of binder in weight. Cu grid was used as the current collector and 1 M LiPF 6 in EC/DEC (EC:DEC = 1:1 in v/v) was used as the electrolyte. The specifi c capacity was based on the weight of Li 3VO4 in the composite electrode.