Films prepared from high molecular weight chitosan are shown to exhibit the highest electrical conductivity of 2.14 x 10(-7) S cm(-1). The electrical conductivity is further enhanced to 1.03 x 10(-5) S cm(-1) when ethylene carbonate (EC) is used as a plasticizer. X-ray diffraction (XRD) shows that EC disrupts the crystalline nature of chitosan acetate. Infrared (IR) spectroscopy reveals a shift in the amide band from 1590 to 1575 cm(-1) on addition of LiCF3SO3. A film with a (chitosan + 0.4 g EC) to LiCF3SO3 ratio of 80:20 gives the highest electrical conductivity of 3.0 x 10(-4) S cm(-1). This film is used as an electrolyte for the fabrication of chitosan-based secondary cells, viz., Li/chitosan-EC-LiCF3SO3/V2O5. The characteristics of the cells are presented in this paper.