Knowledge of ion-conduction mechanisms in polymers is important for designing better polymer electrolytes for electrochemical devices. In this work, chitosan-ethylene carbonate/propylene carbonate (chitosan-EC/PC) system with lithium acetate (LiCH3COO) and lithium triflate (LiCF3SO3) as salts were prepared and characterized using electrochemical impedance spectroscopy to study the ion-conduction mechanism. It was found that the electrolyte system using LiCF3SO3 salt had a higher ionic conductivity, greater dielectric constant and dielectric loss value compared to system using LiCH3COO at room temperature. Hence, it may be inferred that the system incorporated with LiCF3SO3 dissociated more readily than LiCH3COO. Conductivity mechanism for the systems, 42 wt.% chitosan-28 wt.% LiCF3SO3-30 wt.% EC/PC (CLT) and 42 wt.% chitosan-28 wt.% LiCH3COO-30 wt.% EC/PC (CLA) follows the overlapping large polaron tunneling (OLPT) model. Results show that the nature of anion size influences the ionic conduction of chitosan based polymer electrolytes. The conductivity values of the CLA system are found to be higher than that of CLT system at higher temperatures. This may be due to the vibration of bigger triflate anions would have hindered the lithium ion movements. FTIR results show that lithium ions can form complexation with polymer host which would provide a platform for ion hopping. (C) 2015 Elsevier Ltd. All rights reserved.