Poly(ethylene oxide) has been intercalated inside the interlayer galleries of montmorillonite clay and the electrochemical properties of the nanocomposite have been investigated. Interlayer spacing and clay gallery width increase with increasing MMT concentration confirming intercalation of PEO into MMT as observed from XRD results. The fraction of free anions as calculated from FTIR, increases with increasing clay content and remains constant beyond 7.5 wt. % of clay content. Ionic conductivity of the order of 10⁻⁴ Scm⁻¹ has been obtained in the case of MMT based electrolytes. The initial increase of conductivity with increasing MMT content can be attributed to the increase fraction of free ions which eventually increases ionic conductivity. After 7.5 wt. % of MMT loading ionic conductivity decreases due to the high viscosity of MMT. Interfacial stability results show that passivation takes place very slowly in MMT based electrolytes. Dielectric properties show that at high frequency relaxation takes place due to the segmental motion of polymer chains and it proves the hopping of ions.