WO3 thin films were deposited on ITO/PET substrates by DC magnetron reactive sputtering at different glancing angles. The surface and cross-section morphology as well as chemical composition of WO3 thin film were characterized by field emission scanning electron microscope (FE-SEM) and energy dispersive spectrometer (EDS); Electrochemical and optical performances were measured by electrochemical workstation and ultraviolet spectrophotometer. The results show that the film surface forms a mountain-like morphology as the glancing angle 60, and the cross-section presents slant nano-columnar structure, which is benefit to the migration of ions and electrons. As the glancing angle =80, WO3 thin film has the fastest ion diffusion rate and the largest light modulation amplitude. The colorization efficiency reaches to 27.05cm2/C. Furthermore, the film also shows fast response and good cycle stability.