In this work, the polymer electrolytes prepared utilizing rice starch with incorporation of sodium iodide (NaI) and MPII ionic liquid. The effect of MPII ionic liquid on ionic conductivity, structure and thermal properties is studied using electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FTIR), X-Ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The solid polymer electrolyte-based dye sensitized solar cells were fabricated and analyzed under Sun simulator.