Li2−x VTiO4/C sample with a disordered rock salt structure was successfully prepared by annealing at a temperature of 850°C. The electrochemical oxidation in the first cycle occurs at voltages above 4V vs. metallic lithium, while the shapes of the electrochemical curves in consequent reduction–oxidation processes show a monotonous change of the potential between the selected cut-off voltages. A linear combination fit of individual XANES spectra was used for the determination of the oxidation states of as prepared sample and intermediate states during oxidation and reduction. In the as-prepared sample, vanadium was found to be in the average oxidation state of V3.5+ and was additionally oxidized to V3.8+ by the electrochemical charging. During the discharge process, the vanadium oxidation state was reduced to V3.0+. In situ X-ray diffraction patterns and EXAFS analysis suggest good structural stability during oxidation and reduction, which is also reflected in the cycling stability if batteries were cycled in the voltage window between 2.0V and 4.4V. Extension of the lower cut-off voltage to 1.0V doubles the capacity retention with the improved capacity stability if compared with several high capacity vanadium based materials.