The blend-based polymer electrolyte consisting of poly (vinyl chloride) (PVC) and poly (ethylene glycol) (PEG) as host polymers and lithium perchlorate (LiClO4) as the complexing salt was studied. An attempt was made to investigate the effect of TiO2 concentration in the unplasticized PVC-PEG polymer electrolyte system. The XRD and FTIR studies confirm the formation of a polymer-salt complex. The conductivity results indicate that the incorporation of ceramic filler up to a certain concentration (15 wt.%) increases the ionic conductivity and upon further addition the conductivity decreases. The maximum ionic conductivity 0.012∈×∈10 -4 S cm-1 is obtained for PVC-PEG-LiClO 4-TiO2 (75-25-5-15) system. Thermal stability of the polymer electrolyte is ascertained from TG/DTA studies. © 2008 Springer-Verlag.