<p>In this study, the role of potato starch replacement with fish skin gelatin (FSG) on ion transport parameters has been studied in chitosan (CS) based solid electrolyte. The CS:FSG host doped with various KSCN salt concentrations as an ionic provider. The solid films were characterized for their structural and electrical properties. The results of XRD analysis revealed an increase in the amorphous phase at dopant salt concentrations of up to 40 wt%. The broadening of the FTIR spectroscopy bands and a decrease in intensity confirmed the favorable interactions among the components of the biopolymer blend electrolytes. Electrochemical Impedance spectroscopy (EIS) was conducted over a wide frequency range to examine the films’ electrical behavior. The results of real and imaginary parts of impedance were analyzed using an equivalent circuit model. The characteristics of ion transport, including mobility (<i>μ</i>), carrier density (<i>n</i>), and diffusion coefficient (<i>D</i>), were precisely assessed by examining free ions, contact ion pairs, and ion aggregates through the analysis of both deconvoluted FTIR spectra and impedance-based approaches. Additionally, dielectric properties were analyzed to understand the polarization of ions and loss phenomena. The contribution of DC conductivity to dielectric loss was found to be higher than to the dielectric constant. The dielectric properties were found to be improved by the addition of salt, as evidenced by the dispersive relaxation characteristics that confirmed the non-Debye behavior of the solid polymer electrolyte films. This behavior was further supported by the emergence of a deformed arc in the Argand plot. In line with the findings of the EIS and AC conductivity tests, it was observed that the relaxation period was reduced when the salt concentration increased. Electric modulus was investigated on impedance data to minimized the electrode polarization effects. The relaxation time were evaluated from both <InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(\text{tan}\delta\)</EquationSource> </InlineEquation> and <InlineEquation ID="IEq2"> <EquationSource Format="TEX">\({M}^{{\prime}{\prime}}\)</EquationSource> </InlineEquation> spectra to distinguish relaxation processes associated with ion hopping and conductivity relaxations respectively. The various functional groups found in FSG improve ion dissociation and transport, making it more compatible with KSCN than PS. This results in an improved ionic conductivity of <InlineEquation ID="IEq3"> <EquationSource Format="TEX">\(5.10\times {10}^{-5}{ S cm}^{-1}\)</EquationSource> </InlineEquation> at 40 wt% of KSCN at room temperature.</p>