Polymer-layered silicate nanocomposite electrolytes (PLSNEs) were prepared by utilizing a biodegradable polymer namely poly(ϵ-caprolactone) as host polymer and zinc triflate as dopant salt with the incorporation of varying concentrations of octadecylamine modified montmorillonite nanoclay and further characterized using various experimental techniques. A maximum conductivity of 9.5×10−5 Scm−1 was achieved for a 15wt% loading of the nanoclay. X-ray diffraction and differential scanning calorimetric studies revealed the change occurring in the crystalline behavior of the electrolyte as a result of incorporation of the nanoclay. An appreciably good thermal and electrochemical stability was also observed thus suggesting applicability of the prepared electrolyte in commericial systems and therefore the feasibility of reduction and oxidation processes of MnO2 cathode with the prepared electrolyte system has also been evaluated by means of cyclic voltammetry. The best conducting sample of the polymer electrolyte showed a remarkable degradability over a degradation period of 90 days in soil compost.