In this study, a freestanding thin film composed of lithium triflate (LiTf) salt (30-40 wt.%) and epoxidized-30% poly (methyl methacrylate)-grafted natural rubber (EMG30) (50, 54.6, 62.3 mol %) were prepared by a solvent cast technique. The EMG30 were found to increase the ionic conductivity of EMG30-LiTf by one order of magnitude compared to MG30-LiTf. The highest ionic conductivity achieved was 5.584 x10-3Scm-1at room temperature when 40 wt.% of LiTf salts were introduced into 62.3 mol % EMG30. The ionic conduction mechanisms in EMG30-LiTf electrolytes obey Arrhenius rule in which the ion transport in these materials is thermally assisted.