The investigation of chemically cross-linked, self-supporting gel-type electrolyte membranes, based on hybrid polyfluorosilicone polymers reinforced with nanosized silica, for lithium-ion battery systems is reported. The polyfluorosilicone materials were selected on the basis of their high chemical and thermal stabilities. The precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional polymer matrices. The latter were undergone to swelling processes in (non-aqueous, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. Several kinds of membranes, based on different types of polyfluorosilicone precursor, were prepared and characterized in terms of swelling behavior, ionic conductivity and electrochemical stability. The properties of the swelled matrices were evaluated as a function of dipping time, temperature, kind of electrolytic solution and cross-linking initiator content.