Sodium-ion conduction-based blend polymer films have been developed with the incorporation of amino acid and L-phenylalanine for electrochemical storage device applications. The X-ray diffraction and Fourier transform infrared spectroscopy techniques are used to characterize the structural identification, which concerns enhancing the ionic movement and the existence of ions in blended polymer with the interaction of amino acid and salt. Variations in asymmetrical and symmetrical stretching vibrations of ions were investigated by the appeared partition peaks of FTIR in absorbance mode. Electrical impedance analysis has explained the microstructural properties of polymers through the complex impedance spectra. The enhanced electrical conductivity of 2.56 910$^{-5}$ S cm$^{-1}$ has been identified for 2.5 wt% of L-phenylalanine added blend polymer electrolyte system at ambient temperature. From the frequency dependence conductivity analysis, ${\sigma}_{dc}$ values are calculated from Jonscher’s power law. In temperature-dependent conductivity analysis, two different types of activation energies are obtained for lower and higher temperatures. The dielectric and loss tangent analyses are also calculated and analysed the relaxation process based on the hopping mechanism. The electrochemical stability of higher conductivity solid polymer electrolytes is also verified by cyclic voltammetric analysis.