Solid polymer electrolyte (SPE) can be viewed as an alternative of conventional liquid electrolyte since it is easier to handle. In the present work, starch/chitosan-ammonium nitrate (NH4NO3) SPE has been prepared by solution casting technique. Different amount of 1-ethyl-3-methylimidazolium nitrate ([EMIM][NO3]) was added to the sample. Ionic conductivity analysis was conducted over a wide range of frequency between 50 Hz-1 MHz using impedance spectroscopy to evaluate the dielectric properties and conductivity of the sample. Sample with 15 wt% of [EMIM][NO3] has shown the highest conductivity of 7.36 � 10-5 S cm-1 at room temperature. Complex permittivity for real (?r), imaginary (?i) and electrical modulus for real (Mr) and imaginary (Mi) part was determined and plotted. � 2016 Trans Tech Publications, Switzerland.