Cross-linked, self-supporting, membranes for lithium ion battery gel electrolytes were obtained by cross-linking a mixture of polyfluorosilicone (PFSi) and polysilicone containing ethylene oxide (EO) units [P(Si-EO)]. The membranes were also reinforced with nanosized silica. The two polymer precursors were synthesized with functional groups capable to form inter-molecular cross-linking, thus obtaining three-dimensional, polymer matrices. The precursors were dissolved in a common solvent and cross-linked to obtain free-standing PFSi/P(Si-EO):SiO2 composite films. The latter were undergone to swelling processes in (non-aqueous, aprotic, lithium salt containing) electrolytic solutions to obtain gel-type polymer electrolytes. The properties of the swelled PFSi/P(Si-EO):SiO2 samples were evaluated as a function of the electrolytic solutions and the dipping time. The PFSi/P(Si-EO):SiO2 membranes exhibited large swelling properties, high ionic conductivity and good electrochemical stability.