Inverse spinel LiNiVO4 thin films were prepared by rf-sputtering, fallowed by films annealed at 300, 450 and 600°C for 2h to induce the crystallization of the films. The films were characterized by X-ray diffraction, Rutherford backscattering spectroscopy, nuclear reaction analysis, Auger electron spectroscopy, atomic force microscopy and scanning electron microscope techniques. The Anodic electrochemical performance films have been cycled in the range of 0.02–3.0V, at room temperature, at a current density 75μAcm−2. Galvanostatic cycling and cyclic voltammetry results shows characteristic cycling curves with respect to annealing temperature. The films annealed at 450°C showed best electrochemical performance and excellent capacity retention during cycling was observed due to its nanosized morphology.