Hexanoyl chitosan that exhibited solubility in THF was prepared by acyl modification of chitosan. Films of hexanoyl chitosan-based polymer electrolyte were prepared by the technique of solution casting. The effect of plasticizers on the electrical properties of hexanoyl chitosan: LiCF3SO3 electrolytes have been investigated. The plasticizers used were EC, PC and a mixture of EC and PC. The highest room temperature conductivity of about 1.1 x 10-4 S cm-1 was achieved for electrolyte with composition of 50:50 (wt.%) mixture of PC: EC. The variations in conductivity have been explained using the Rice and Roth model from which the numbers of free ions per unit volume, mobility and diffusion coefficient of free ions were obtained. Electrochemical cells based on LiCoO2/MCMB couple were assembled using the electrolyte that exhibited the highest ionic conductivity. The performance of the cells have been studied and discussed in this paper.