The polymer electrolyte system of chitosan/dextran-NaTf with various glycerol concentrations is prepared in this study. The electrical impedance spectroscopy (EIS) study shows that the addition of glycerol increases the ionic conductivity of the electrolyte at room temperature. The highest conducting plasticized electrolyte shows the maximum DC ionic conductivity of 6.10 × 10⁻⁵ S/cm. Field emission scanning electron microscopy (FESEM) is used to investigate the effect of plasticizer on film morphology. The interaction between the electrolyte components is confirmed from the existence of the O–H, C–H, carboxamide, and amine groups. The XRD study is used to determine the degree of crystallinity. The transport parameters of number density (n), ionic mobility (µ), and diffusion coefficient (D) of ions are determined using the percentage of free ions, due to the asymmetric vibration (υ_as(SO₃)) and symmetric vibration (υ_s(SO₃)) bands. The dielectric property and relaxation time are proved the non-Debye behavior of the electrolyte system. This behavior model is further verified by the existence of the incomplete semicircle arc from the Argand plot. Transference numbers of ion (t_ion) and electron (t_e) for the highest conducting plasticized electrolyte are identified to be 0.988 and 0.012, respectively, confirming that the ions are the dominant charge carriers. The t_ion value are used to further examine the contribution of ions in the values of the diffusion coefficient and mobility of ions. Linear sweep voltammetry (LSV) shows the potential window for the electrolyte is 2.55 V, indicating it to be a promising electrolyte for application in electrochemical energy storage devices.