The electrosynthesis of polypyrrole (PPy) has been achieved on aluminium in aqueous medium of tartaric acid by means of cyclic voltammetry, potentiostatic and galvanostatic techniques. Scanning electron microscopy (SEM) and X-ray microanalysis by energy spectroscopy dispersion (EDS) applying on surfaces show that the PPy coating is developed from the metal surface through the cracks of the initial Al2O3 layer. A mechanism involving the participation of the supporting electrolyte and the pyrrole (Py) in distinct active sites was proposed based on the linear sweep voltammetry. It is observed for all applied electrochemical techniques that the pyrrole concentration has to be higher than 0.1 M to allow the polypyrrole electrodeposition in acid medium. Scanning electron microscopy, secondary electrons (SE) and backscattering electrons (BE), shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. Moreover, EDS reveals a good homogeneity and compactness of the film achieved in galvanostatic method. The corrosion results in 3% NaCl medium show that the PPy coating decreases the corrosion behaviour of the aluminium. The bilayer Al2O3/PPy shows a capacitor with future applications. (c) 2006 Elsevier Ltd. All rights reserved.