Metal oxyfluoride compounds are gathering significant interest as cathode: materials for lithium ion batteries at the moment because of their high theoretical capacity and resulting high energy density. In this regard, a new and direct approach is presented to synthesize phase-pure vanadium oxyfluoride (VO2F). The structure of VO2F was' identified by Rietveld refinement of the powder X-ray diffraction (XRD) pattern. It crystallizes in a perovskite-type structure with-disorder of the oxide and fluoride ions. The as-synthesized VO2F was tested as a cathode material for lithium ion batteries after being surface-coated with few-layer graphene. The VO2F delivered a first discharge capacity of 254 mA h g(-1) and a reversible capacity of 208 mA h g(-1) at a rate of C/20 for the first 20 cycles with an average discharge voltage. of 2.84 V, yielding an energy density of 591 W h kg(-1). Improved rate capability that outperforms the previous report, has been achieved, showing a discharge capacity of 150 mA h g(-1) for 1 C. The structural changes during-lithium insertion and extraction were monitored by ex-situ XRD analysis of the electrodes discharged and charged to various stages. Lithium insertion results-in an irreversible structural change of the anion lattice from 3/4 cubic close packing to hexagonal close packing to accommodate the inserted lithium ions while keeping the overall space-group symmetry. For the first time we have revealed a structural change for the ReO3-type structure of as-prepared VO2F to the RhF3 structure after lithiation/delithiation, with structural changes that have not been observed in previous reports. Furthermore, the new synthetic approach described here would be a platform for the synthesis of new oxyfluoride compounds.