Membranes of sodium bis(trifluoromethanesulfonate) imide (NaTFSI) complexed with poly(ethylene oxide) (PEO) salt have been prepared by a solvent-free hot-pressing technique with different EO:Na molar ratio. All membranes show good ionic conductivities in the range of 10−3 S cm−1 above 70 °C. However, the more NaTFSI-concentrated samples are sticky gums due to the plasticizing nature of the anion. The PEO20:NaTFSI sample exhibits the compromise of conductivity, thermal and mechanical properties. The addition of nanometric SiO2 to the PEO20:NaTFSI membranes further enhances their mechanical properties. Moreover, the PEO20:NaTFSI + 5 wt.% SiO2 membranes show similar ionic conductivity and similar anodic electrochemical stability in comparison to the ceramic free PEO20:NaTFSI sample. In a Na(s)/polymer electrolyte/Na(s) symmetrical cell followed up to 30 days, the presence of the ceramic filler slightly increased the interface resistance in comparison to the ceramic-free membrane. Nuclear magnetic resonance determinations of anion diffusion coefficients and Na+ mobility suggest that presence of filler may have a positive affect on the cation transference number that is in accordance with the t Na + transference number measurement.