Films of composites of chitosan/poly(aminopropyltriethoxysilane)/poly(ethylene oxide) (CHI/pAPS/PEO) containing a fixed amount of lithium salt are studied. The ternary composition diagram of the composites, reporting information on the mechanic stability, the transparence and the electrical conductivity of the films, shows there is a window in which the molecular compatibility of the components is optimal. In this window, defined by the components ratios CHI/PEO 3:2, pAPS/PEO 2:3 and CHI/PEO 1:2, there is a particular composition Li-x(CHI)(1)(PEO)(2)(pAPS)(1.2) for which the conductivity reaches a value of 1.7 x 10(-5) S cm(-1) at near room temperature. Considering the balance between the Lewis acid and basic sites available in the component and the observed stoichiometry limits of formed polymer complexes, the conductivity values of these products may be understood by the formation of a layered structure in which the lithium ions, stabilized by the donors, poly(ethylene oxide) and/or poly(aminopropyltriethoxysilane), are intercalated in a chitosan matrix. (c) 2007 Elsevier Ltd. All rights reserved.