Solid polymer polyethylene glycol (PEG)-based electrolytes composed with zinc acetate Zn(CH3COO)2 have been prepared by using solution blending. We proposed a scheme of PEG–zinc acetate for battery application. The structure confirmation was done by using X-ray diffraction studies detecting the phase variation. The thermal properties demonstrate the optimization of melting point (T m) as a function of loading zinc acetate. The impedance analysis reveals that the role of ionic conductivity depends on the controlled concentration of Zn(CH3COO)2. Optimum ionic conductivity σ ~ 1.55 × 10−6 S cm−1 at room temperature (303 K) was observed for 70:30 composition. The linear variation in log σ vs 1000/T plot is based on the Arrhenius-type thermally activated process. The simultaneous discharge profile was confirmed by the solid-state electrochemical cell. Hence, the PEG–zinc acetate composition was suggested for polymer electrolyte battery application.