This paper reports the characterization of starch-chitosan blend based solid polymer electrolyte (SPE) system and its application in electrochemical double layer capacitor (EDLC) and proton batteries. All the SPEs are prepared via solution cast technique. Results from X-ray diffraction (XRD) verify the conductivity result from our previous work. Scanning electron microscopy (SEM) analysis shows the difference in the electrolyte's surface with respect to NH4Cl and glycerol content. From transference number measurements (TNM), transference number of ion (tion ) of the electrolytes shows that ion is the dominant conducting species. Transference number of cation (t+ ) for the highest conducting electrolyte is found to be 0.56. Linear sweep voltammetry (LSV) result confirms the suitability of the highest conducting electrolyte to be used in the fabrication of EDLC and proton batteries. The EDLC has been characterized using cyclic voltammetry (CV) and galvanostatic charge-discharge measurements. The open circuit potential (OCP) of the primary proton batteries for 48h is lasted at (1.54±0.02)V, while that of secondary proton batteries is lasted at (1.58±0.01)V. The primary proton batteries have been discharged at different constant currents. The secondary proton battery has been charged and discharged for 40 cycles.