Polypyrrole films were electrodeposited at pure aluminium from aqueous solution of sodium sulphate containing pyrrole and organic compounds as dopants. Substrate-adherent polypyrrole films were obtained by electrochemical oxidation of pyrrole using the potentiodynamic method and cycling the electrode potential from 50 up to 100 cycles on the potential range of 0 divided by 800 mV. Since the conducting polymers, such as polypyrrole, are electrosynthesized easily at inert electrodes such as gold and platinum, but much more difficult at aluminium electrodes, the surface protective oxide, Al2O3, was removed, as it acts as a barrier inhibiting electron transfer and the polymerization process. The electrochemical properties of polypyrrole films electrosynthesized from aqueous solutions containing sodium dodecylsulphate (SDS) and sodium bis(2-ethylhexyl) sulfosuccinate (AOT) as doping electrolytes were studied by cyclic voltammetry and electrochemical impedance spectroscopy. The results indicate that the mechanism of the redox process is complex and may be governed by the diffusion of the electrolyte. The cyclic voltammograms of polypyrrole film synthesized in solutions having different concentrations of SDS and AOT indicate that the dopant concentration plays a very relevant role in the electrochemical response of the doped polypyrrole films like as: PPY/SDS/aluminium oxide and PPY/AOT/aluminium oxide. The results indicate that the SDS and AOT anions favor redox processes which are faster and more reversible than those associated to usual polypyrrole electrodes. However, the aluminium substrate had a considerable effect on the electrochemical activity of the polypyrrole films and that, because in the presence of pyrrole, anodization of these electrolytes resulted in formation of Al2O3 and PPY layers simultaneously. This is consistent with a galvanic interaction between the polymer and the aluminium substrate, giving rise to oxidation of the aluminium and reduction of the polymer. The corrosion performance of polypyrrole coated aluminium was evaluated by DC polarization and Electrochemical Impedance Spectroscopy. Our results show that the presence of polypyrrole coatings significantly increases the corrosion potential and drastically reduces the corrosion current and corrosion rate of pure aluminium. The corrosion resistance of polypyrrole coated aluminium was higher than of uncoated aluminium.