Electrochemical analysis of alpha-LixWO3 films of 400 nm thick prepared by electron beam evaporation technique over ITO substrates are reported. The chemical potential variation with the fraction of inserted lithium, mu(x), was obtained by chronopotentiometry measurements in quasiequilibrium conditions and the chemical capacitance, C-ch proportional to partial derivativex/partial derivativemu, was determined. A power-law dependence C-ch proportional to x(a) (a approximate to 0.65) was observed for x>10(-3). indicating a wide distribution of site energies. Additionally, impedance measurements at different stages of insertion gave information on the variation of the chemical diffusion coefficient D-ch with potential (composition). Impedance spectra were analyzed by means of a spatially restricted diffusion model. D-ch was found to vary in the range 10(-10)-10(-12) cm(2) s(-1) nearly proportional to the inverse of composition, D-ch proportional to 1/x. This suggests that ion transport process is considerably influenced by the extent of intercalation. (C) 2004 Elsevier B.V. All rights reserved.