Films of hexanoyl chitosan containing lithium perchlorate (LiClO₄) or lithium triflouromethanesulfonate (LiCF₃SO₃) were prepared by solution casting technique. The effect of anion size on the conductivity behaviour of hexanoyl chitosan has been investigated. The conductivity of 4.15 × 10^-7S/cm and 4.07 × 10^-6S/cm were achieved for the hexanoyl chitosan-LiClO₄and hexanoyl chitosan-LiCF₃SO₃electrolyte system at 50wt.% of salt concentration, respectively. The Rice and Roth model was used to analysis quantitatively the obtained conductivity trends for the prepared electrolyte systems. The diffusion coefficients of cations and anions were calculated from the conductivity and transference number measurements. This is followed by the discussion on the diffusion coefficients of ClO₄^-and CF₃SO₃^-anion.