Hexanoyl chitosan-based polymer electrolytes were prepared using the solution casting technique. The effect of dimethyl carbonate (DMC) plasticizer on the structural and electrical properties of the prepared electrolyte system was investigated by X-ray diffraction and impedance spectroscopy, respectively. Upon addition of 15 wt. % of DMC, the ionic conductivity was increased to 4.09 x 10^-4 S cm^-1 from 3.06 x 10^-4 S cm^-1. The XRD results revealed the variation in conductivity from the structural aspect. For example, sample with lower crystallinity exhibits higher conductivity. The Rice and Roth model was employed to understand the variation in conductivity on the basis of number and mobility of free ions.