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This paper provides a comprehensive overview of the influence of 1-Butyl-1-Methylpyrrolidinium Trifluoromethanesulfonate (BMPyrrOTf)-ionic liquid on a new polymer electrolyte where Polyethylene oxide (PEO) as host and ammonium iodide (NH4I) as salt. These IL-doped solid polymer electrolyte were prepared using solution cast technique. Various characterisation techniques have been utilized to evaluate the qualitative and quantitative estimation of polymer electrolyte like Polarized microscopy (POM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Linear sweep voltammetry (LSV), Ionic transference no. (tion) and Impedance spectroscopy. Doping IL increases conductivity and highest achieve at 8 wt% of BMPyrrOTF with conductivity value reaches upto 4.15 × 10–5 S/cm at. Using Wagner’s polarization method, Ionic transference measurement support ionic conduction while stable potential window has further affirmed good electrochemical stability of films. The highest conducting IL-enriched polymer electrolyte sandwiched low-cost dye-sensitized solar cells (DSSCs) and electric double layer capacitors (EDLCs) have been developed, and their performance is conveniently appropriate.