Plasticised polymer blend electrolytes based on poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-co-HFP) and poly(ethyl methacrylate) (PEMA) were prepared for different lithium salts LiX (X=ClO4, CF3SO3, BF4 and N[CF3SO2]2) using facile solution casting. To confirm the structures and complexations of the electrolyte films, the prepared electrolytes were subjected to XRD and FTIR analysis. TG–DTA was used to ascertain the thermal stability of the electrolytes, and the porous nature of the electrolytes was identified using scanning electron microscopy via ion-hopping conduction. AC impedance analysis was performed for all the electrolyte samples at various temperatures from 303 to 363K. The results suggest that among the various lithium salts, LiN[CF3SO2]2-based electrolytes exhibited the highest ionic conductivity (0.918×10−3 Scm−1). The temperature dependence of the ionic conductivity also complies with the VTF relation.