The main aim of the present work is to optimize highly conducting solid polymer electrolytes by doping of ionic liquid in a Poly-ethylene oxide (PEO) polymer complexed Sodium Iodide (NaI) matrix. Solution casting method has been used to synthezis solid polymer electrolytes. Electrical, thermal, structural, and optical studies confirm the homogenous complexation of polymer electrolytes with ionic liquid. Furthermore, the electric double-layer capacitors (EDLCs) device and Dye Sensitized Solar Cell (DSSC) has been developed using high conducting ionic liquid (IL) polymer electrolyte with maximum conductivity, demonstrating that ionic liquids have a potential possibility to choose as an electrolyte in developed energy devices.