The design of improved materials for electrochromic applications now involves extensive use of novel composites, thus requiring an investigation of the mechanisms responsible for electrochromism in these structures. Using films of WO3 and chitosan produced with the layer-by-layer (LBL) technique, we demonstrate that characteristics such as the number of electrochemical active sites (K), the molar absorption coefficient (epsilon), and the electrochromic efficiency (eta) can be obtained using the quadratic logistic equation (QLE). The complexation ability between chitosan and WO3 allowed the growth of visually uniform multilayers of the composite, with the same amount of material adsorbed in each deposition cycle. By fitting the absorbance changes (Delta A) resulting from the electronic intervalence transfer from W(V) to W(VI) sites in four-bilayer LBL films of WO3/chitosan and WO3/chitosan with ethanol in the precursor dispersion, K was estimated to be ca. 5.5 x 10(-8) mol cm(-1) and 3.6 x 10(-8) mol cm(-2), respectively. The molar absorption coefficient and electrochromic efficiency vary with the charge injected because of the saturation of W(V) sites and the dissipation and feedback effects implicit in the QLE associated with ion-network interactions, such as the proton trapping effect. The LBL film Of WO3/chitosan showed a smaller molar absorption coefficient and electrochromic efficiency than that containing ethanol because of a greater proton trapping effect for the LBL film with no ethanol. This enhanced trapping effect was seen as a decrease in the electronic flux involved in intervalence transfer in electrochemical impedance spectroscopy experiments.