Ion conducting polymer electrolyte films based on poly(ethylene oxide) (PEO) complexed with a glass (15Na(2)O-15NaF-70B(2)O(3)) are prepared by a solution-cast technique. The complexation of the glass with PEO is confirmed by X-ray diffraction analysis. DC conductivity in the temperature range 303-373 K and transference number measurements are performed in order to investigate the charge transport in the polymer electrolyte system. The conductivity of the (PEO + glass) electrolyte is about 10(4) times larger than that of pure PEO at room temperature. The transference number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. Using these polymer electrolytes, solid-state electrochemical cells are fabricated. Various parameters associated with these cells are evaluated and compared with those of other reported cells.