The fabrication of energy storage EDLC in this work is achieved with the implementation of a conducting chitosan-methylcellulose-NH4NO3-glycerol polymer electrolyte system. The simple solution cast method has been used to prepare the electrolyte. The impedance of the samples was fitted with equivalent circuits to design the circuit diagram. The parameters associated with ion transport are well studied at various plasticizer concentrations. The FTIR investigation has been done on the films to detect the interaction that occurs among plasticizer and polymer electrolyte. To get more insights into ion transport parameters, the FTIR was deconvoluted. The transport properties achieved from both impedance and FTIR are discussed in detail. It was discovered that the transport parameter findings are in good agreement with both impedance and FTIR studies. A sample with high transport properties was characterized for ion dominancy and stability through the TNM and LSV investigations. The dominancy of ions in the electrolyte verified as the tion of the electrolyte is established to be 0.933 whereas it is potentially stable up to 1.87 V. The rechargeability of the EDLC is steady up to 500 cycles. The internal resistance, energy density, and power density of the EDLC at the 1st cycle are 53 ohms, 6.97 Wh/kg, and 1941 W/kg, respectively.