In this study polymer electrolytes composed of poly(methyl methacrylate) (PMMA) as a host polymer and ethylene carbonate (EC) as a plasticizer complexed with different lithium salts, i.e. lithium tetrafluoroborate (LiBF4) and lithium triflate (LiCF3SO3) were prepared by the solution casting technique. The conductivities of the films were characterized by impedance spectroscopy. At room temperature, the highest conductivities were 4.07 × 10–7S cm–1 and 3.40 × 10–5 S cm–1 achieved, respectively from the films containing 30 wt% LiBF4 in the PMMA-EC-LiBF4 system and 35 wt% LiCF3SO3 in the PMMA-EC-LiCF3SO3 system. The conductivity-temperature dependence of the films seemed to obey the Arrhenius equation in which the ion transport in these materials was thermally assisted. Scanning electron microscopy analysis showed that the surface of PMMA-EC-LiCF3SO3 film was smooth and homogeneous, hence lithium ions could traverse through the PMMA-EC-LiCF3SO3 film more easily compared to the PMMA-EC-LiBF4 film. X-Ray diffraction studies revealed that complexation had occurred and the complexes formed were amorphous.