Tungsten oxide thin films with different stoichiometry have been deposited on In2O3 : SnO2 glass (ITO) and Si wafer by pulsed laser deposition (PLD) technique at different deposition temperatures and oxygen pressure. The structural properties of WO3 thin films were analyzed by using a scanning accessory of transmission electron microscope (STEM), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), Raman spectrum (RS). Thin films deposited at 200 °C on ITO showed amorphous structure, those deposited at 300 and 400 °C on ITO showed nanocrystalline triclinic structure. As for samples deposited at 400 °C, in which the crystals keep nanocrystalline, cyclic voltammograms at sweep rate of 50 mV/s shows that no long-term degradation was noted at least up to 1000 cycles, and durability was verified to 8000 cycles in the voltage range between —1.2 and 1.4 V. Its open and porous structure is suitable for Li-ions going into and out, and induced improved cycle stability and reversibility.