A free-standing film consisting of 49% PMMA grafted-natural rubber electrolytes was prepared. Potassium hydroxide (KOH) and propylene carbonate (PC) was added to the preparation and the properties of the electrolytes measured using complex impedance analysis at various temperatures. The addition of plasticiser in alkaline polymer electrolyte gives rise to the ionic conductivity up to 2.647 x 10-6 S cm-1 at composition consisting of 50wt.% of PC. The dielectric properties of the GPEs were studied and the relaxations at higher frequencies appear in both imaginary and real part of the permittivity. These relaxations are related with the interface ion polarisations at the polymer-electrode interface and segmental motion of the polymer electrolyte molecular chains. The influence of the impedance spectra on temperature was studied. Results showed rising temperature increased conductivity, top frequency (f*), relative dielectric constant (εr) and geometrical capacitance (Cg) due to the mobility of free ion carriers.