Corn starch (CS) – sodium chloride (NaCl) based polymer electrolytes were prepared by solution casting technique. At room temperature, CS-NaCl film with ratio of 70 wt. % - 30 wt. % demonstrates the highest ionic conductivity in the range of (1.72 ± 0.12) x10-5 Scm-1. Temperature-dependence ionic conductivity study follows Arrhenius model and using related plot, the activation energy for highest conducting composition is 0.16eV. The transport number measurement studies confirmed that the ionic conductivity of this polymer electrolyte is due to ions. Fourier transform infrared spectroscopy (FTIR) analysis proved the interaction between CS and NaCl.