Novel solid polymer electrolyte (SPE) films based on poly(methyl methacrylate) (PMMA) and lithium acetate (CH3COOLi) with different weight ratios of PMMA:CH3COOLi wt% (60:40, 70:30, 80:20 wt%) were prepared by solution casting technique. XRD analysis confirmed the amorphous nature of Li-PMMA SPE films. FTIR analysis revealed the structural changes in polymer by complexation with Li salt. From the optical absorbance studies, the value of lowest energy band gap was found to be 3.06 eV for the composition, PMMA:CH3COOLi (60:40 wt%). From AC impedance studies, the highest value of ionic conductivity 8.21 x 10(-5) S/cm at 303 K for the SPE film PMMA:CH3COOLi (60:40 wt%) is observed compared to the reported literature. From the results of Li-PMMA SPE film with high ionic conductivity, it is a promising material for the application of solid-state battery.