An investigation is carried out on gel polymer electrolytes consisting of poly (vinylidene fluoride) (PVdF) as a host polymer, lithium perchlorate (LiClO4), lithium triflate (LiCF3SO3) as salts and mixture of ethylene carbonate (EC) and propylene carbonate (PC) as plasticizers. Polymer thin films were prepared by solvent casting technique and the obtained films were subjected to different characterizations, to confirm their structure, complexation and thermal changes. X-ray diffraction revealed that the salts and plasticizers disrupted the crystalline nature of PVdF based polymer electrolytes and converted them into an amorphous phase. TG/DTA studies showed the thermal stability of the polymer electrolytes. The role of interaction between polymer hosts on conductivity is discussed using the results of a.c. impedance studies. Room temperature (28°C) conductivity of 2.786 × 10-3 Scm-1 was observed in PVdF (24)-EC/PC (68)-LiCF3SO3 (2)/LiClO4 (6) polymer system. © Indian Academy of Sciences.