Polyaniline films were electrodeposited at pure aluminium from a tosylic acid solution containing aniline. These polymer films exhibited similar characteristics as pure polyaniline electrosynthesized at an inert platinum electrode, when removed from their respective substrates and dissolved in NMP. Both polymers had similar molecular weights and similar UV-visible absorption spectra. However, the aluminium substrate had a considerable effect on the electrochemical activity of the films. The polyaniline films deposited at aluminium appeared to lose electroactivity and the electrochemical impedance data were governed by the oxidized aluminium substrate. 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 polyaniline deposits appeared to offer only a slight increase in the corrosion resistance of aluminium. Surface potential measurements, using a scanning vibrating probe, showed that attack initiated underneath the polymer under anodic polarization conditions, indicating that chloride anions diffuse across the polymer to react at the underlying aluminium substrate.