Films of an ion conducting, polyblend electrolyte based on (polyvinyl pyrrolidone (PVP)+polyvinyl alcohol (PVA)) complexed with KIO3 are prepared by a solution–cast technique. Measurements of dc conductivity and transference number are made to investigate the order of conductivity and the charge transport in this polyblend electrolyte. Transference number values show that the charge transport in this electrolyte is predominantly due to ions (t ion=0.97). The magnitude of conductivity increases with increase in the concentration of the salt and temperature. Using this electrolyte, electrochemical cells are fabricated and their discharge characteristics are studied under different loads. The results show that KIO3 polyblend electrolytes offer interesting alternatives to other solid-state battery systems. The electrochemical decomposition potential (ECDP) is determined for the polyblend electrolyte. From the ECDP studies, the values of open-circuit voltage (OCV) are calculated and are in good agreement with those obtained from discharge studies.