A series of new Chitosan/poly(mercaptopropysiloxane) hybrid films were obtained by blending mercaptopropylsiloxane oligomers (pMPS) with chitosan (CHI). The MPS oligomers were prepared by sol-gel using as precursor 3-(mercaptopropyl)-trimethoxysilane. The products were characterized by chemical, spectroscopic and morphological methods. Comparison of the thermal stability and FT-IR spectra of the films with those of the pure components indicates the formation of macromolecular aggregates with peculiar properties, different from those of their components. Scanning electron micrographies of the films revealed an organized microscopic pattern suggesting the existence of systematic interactions among their components.