Chitosan + poly(ethylene oxide) mixtures and films prepared from these mixtures were studied by rheological, absorption of solvent vapors, SANS, and mechanical testing methods. At a stoichiometric chitosan:poly(ethylene oxide) monomer:monomer composition, the mechanical properties of chitosan + poly(ethylene oxide) film are the best as compared with those of the initial components or of other compositions. This film composition is shown to be less heterogeneous. Chitosan and poly(ethylene oxide) are proved to be slightly incompatible polymers. This is supposed to induce the two components to align and to order at their stoichiometric composition, leading to the improvement in the mechanical properties.