The effect of sodium nitrate (NaNO₃) salt on the conductivity of polymer system based on the bio polymer cellulose acetate (CA) has been analysed in this study. The films were prepared by solution casting technique. The sample (CA: NaNO3) with the weight ratio of (0.6:0.4) gram exhibited the highest room temperature conductivity of the order 10^-6 Scm^-1. Dielectric measurements were made using ac impedance analyser in the frequency range of 10 Hz–4 MHz. It was observed that the ionic conductivity increased with the increase in salt concentration as well as temperature. The conductivity–temperature relationship was found to obey Arrhenius rule. The activation energy is calculated for the highest conducting sample.