Stable and homogeneous mica-like vanadium pentoxide (V2O5)-nanostructured thin films are prepared directly by simple anodic deposition from V2O5/H2O2 sol solution, and then dried at ambient temperature and annealed at 500 °C in air for 1 h. The films' crystal- and microstructures, surface morphology and Li-ion intercalation properties were characterized and analyzed by X-Ray diffraction (XRD), field emission scanning electron microscopy (FSEM), thermogravimetric analysis (TGA), and electrochemical techniques. When used as a lithium-ion battery (LIB) cathode, the films exhibit a large discharge capacity of 596 mAh g−1 at a current density of 1080 mA g−1, as well as excellent cyclic stability and a fading rate of 1% per cycle. Explanations for such significant enhancements in specific capacity, cyclic stability, and rate performance of mica-like V2O5-nanostructured thin films are demonstrated in this study.