The stability of magnesium and its hydride (Mg/MgH2) against moisture and oxygen can be improved by forming a multilayered structure with a protective polymeric layer. Herein, we report for the first time the fabrication of such a multilayered structure via an electrochemical deposition method consisting of the successive depositions of Mg on electropolymerised polypyrrole (PPy) films. The thickness of the PPy and the Mg layers was similar to 1 mu m, which is larger than the Mg/Pd multilayers prepared via physical deposition methods, owing to the higher surface roughness of electropolymerised films. However, such films displayed remarkable hydrogen storage properties. Hydrogenation of the PPy/Mg film was achieved at 100 degrees C and hydrogen release started from 125 degrees C with a peak at similar to 215 degrees C. When covered by a second PPy layer, the hydrogen desorption temperature increased slightly to 230 degrees C. These hydrogen absorption and desorption temperatures are significantly lower than that of pristine Mg/MgH2 micron sized powders and this was achieved without any additional catalyst. Furthermore, such hydrogenated PPy/Mg/PPy film structures were found to be stable in air even after one week. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.