Polymer electrolytes (PE) comprised of poly(c-caprolactone) (PCL), ethylene carbonate (EC) and ammonium thiocyanate (NH4SCN) were prepared by solution casting. Thermal properties, conductivity and structural studies were characterized by differential scanning calorimetry (DSC), impedance spectroscopy and X-ray diffraction (XRD), respectively. EC is intended to be used as plasticizing solvent to enhance the conductivity. It is found later that EC can also promote ion dissociation in polymer electrolyte system. From DSC studies, the introduction of EC as additive into PCL-NH4SCN complexes reduces the T-m from 56.4 degrees C to 44.1 degrees C. drops T-g from -59.7 degrees C to -76.7 degrees C and suppresses the crystallinity. The conductivity of PE improves from 4.6 x 10(-8) S cm(-1) to 3.8 x 10(-5) S cm(-1) at 50 wt.% EC. Relative permittivity studies show that EC contributes to higher dissociation rate of charge ions. In the temperature dependence conductivity analysis, VTF equation fits very well with regression value close to unity for all the samples demonstrating a close coupling between the conductivity and the polymer segment mobility. The pre exponential factor A increases as more EC is added, reflecting the growth in the number of charge carriers. Structural analysis using XRD displays an apparent reorganization of polymer matrix due to the EC effect. This is in agreement with DSC and EIS observations. Degree of crystallinity calculated using XRD two phase model shows a decrease from 32.7% of zero EC to 16.0% of 50 wt.% EC. These results are comparable to the DSC analysis. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.