Transparent lithium-ion conducting films were prepared by adding lithium perchlorate to a mixture of chitosane (CHI) and poly(aminopropylsiloxane) (pAPS) in a molar ratio 0.6:1 by sol–gel methods. The morphological and molecular properties, determined by scanning electron microscopy and FT-IR, respectively, depend on the lithium salt concentration. The same techniques were also used for performing a “titration” of the capacity of the film for incorporating lithium salt. Results show that about 0.8 mol lithium salt per mol chitosane can be added before the product losses the transparence and molecular compatibility characteristic of the pristine CHI/pAPS polymer complex. When lithium salt addition reaches the tolerance limit, anisotropically oriented patterns are observed in the hybrid films. Both transparence and ionic conductivity of the product appear to be related to the layered nature of formed nanocomposites. The properties of obtained films may be furthermore rationalized considering the chemical functionality and the Lewis donor–acceptor affinity of the components.