Layer-by-layer (LbL) nanocomposite films from TiO2 nanoparticles and tungsten-based oxides (WOxHy), as well as dip-coating films of TiO2 nano particles, were prepared and investigated by electrochemical techniques under visible light beams, aiming to evaluate the lithium ion storage and chromogenic properties. Atomic force microscopy (AFM) images were obtained for morphological characterization of the Surface of the materials, which have similar roughness. Cyclic voltammetry and chronoamperometry measurements indicated high storage capacity of lithium ions in the LbL nanocomposite compared with the dip-coating film, which was attributed to the faster lithium ion diffusion rate within the self-assembled matrix. On the basis of the data obtained from galvanostatic intermittent titration technique (GITT), the values of lithium ion diffusion coefficient (D-Li) for TiO2/WOxHy were larger compared with those for TiO2. The rate of the coloration front in the matrices was investigated using a spectroelectrochemical method based oil GITT, allowing the determination of the "optical" diffusion coefficient (D-op) as a function of the amount of lithium ions previously inserted into the matrices. The Values of D-Li and D-op suggested the existence of phases with distinct contribution to lithium ion diffusion rates and electrochromic efficiency. Moreover, these results aided a better understanding of the temporal change of current density and absorbance during the ionic electro-insertion, which is important for the possible application of these materials in lithium ion batteries and electrohromic devices.