Chitosan has been successfully incorporated as a filler in a polyethylene oxide (PEO) and lithium trifluoromethanesulfonate (LiCF3SO3) matrix with a combination of plasticizers, namely 1,3-dioxolane (DIOX) and tetraethylene glycol dimethylether (TEGDME). The composite gel-polymer electrolyte (CGPE) membranes were prepared by solution casting technique in an argon atmosphere. The prepared membranes were subjected to SEM, TG/DTA and FT-IR analyses. A Li/CGPE/Li symmetric cell was assembled and the variation of interfacial resistance was measured as a function of time. The lithium transference number (Li+t) was measured and the value was calculated as 0.6 which is sufficient for battery applications. The electrochemical stability window of the sample was studied by linear sweep voltammetry and the polymer electrolyte was found to be stable up to 5.2 V.