Present work shows results of Li+ ions insertion and extraction from vanadium pentoxide doped with 5 mol% of molybdenum trioxide (V2O5:MoO3) thin films. The characterizations were performed by cyclic voltammetry (CV), potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The obtained results revealed Li+ diffusional behavior for anodic and cathodic processes, and it was found that Li+ diffusion coefficient (D) values obtained from CV, PITT, and EIS varied from 10(-10) to 10(-12) cm(2) s(-1). Finally, a diffusion of Li+ process was modeled by solving Fick equation with constant D in plane sheet geometry.