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A sodium ion conducting polymer electrolyte based on poly (vinyl alcohol) (PVA) complexed with sodium bromide (NaBr) was prepared using solution cast technique. Several experimental techniques such as XRD, FTIR, SEM, temperature-dependant conductivity and transference number measurements have been performed. XRD and FTIR studies confirm the complexation of salt with the polymer. Surface morphology was studied using Scanning Electron Microscopy. DC conductivity was measured in the temperature range of 303-373 K, and the conductivity was found to increase with the increase of dopant concentration as well as temperature. Transference number data suggests that the charge transport in this polymer electrolyte system is mainly due to ions. Using these polymer electrolyte films, electrochemical cells were fabricated with configuration Na/ (PVA:NaBr)/V 2 O 5 and Na/(PVA:NaBr)/(I2+C+electrolyte) and their discharge characteristics like open circuit voltage (OCV), short circuit current (SCC), power density, energy density were evaluated and compared.