Single salt polymer electrolytes based on hexanoyl chitosan-ENR25 were prepared by employing LiN (CF 3 SO 2 ) 2 or LiCF 3 SO 3 as the doping salt. Elastic property of hexanoyl chitosan was enhanced with the incorporation of ENR25. DSC studies revealed immiscibility of hexanoyl chitosan and ENR25, and dissolution of salt was favored in ENR25 phase. Conductivity enhancement was observed in the blends as compared with the neat hexanoyl chitosan. The maximum conductivities achieved for LiCF 3 SO 3 - and LiN (CF 3 SO 2 ) 2 -comprising electrolyte systems were 1.6 × 10 −8 and 5.0 × 10 −7 S cm −1 , respectively. Deconvolution of spectra bands in the v as (SO 2 − ) mode of LiN (CF 3 SO 2 ) 2 and v s (SO 3 − ) mode of LiCF 3 SO 3 has been carried out to estimate the relative percentage of free ions and associated ions. The findings were in good agreement with conductivity results. Electrical double layer capacitor (EDLC) was fabricated with hexanoyl chitosan/ENR25 (90:10)-LiN (CF 3 SO 2 ) 2 -EmImTFSI electrolyte and activated carbon-based electrodes. The conductivity and electrochemical stability window of hexanoyl chitosan/ENR25-LiN (CF 3 SO 2 ) 2 -EmImTFSI were ~10 −6 S cm −1 and 2.7 V, respectively. The performance of the EDLC was analyzed by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD). From GCD, the specific capacitance of EDLC was 58.0 F g −1 at 0.6 mA cm −2 . The specific capacitance was found to decrease with increasing current density.