The role that Al3Fe intermetallic inclusions play during initiation of pitting corrosion on aluminum alloys was investigated in 0.6 M NaCl. In aerated solutions microscopic observations showed the growth of cavities in the host metal adjacent to inclusions. The rest potential of synthetic Al3Fe was measured in aerated and deaerated NaCl solutions over a range of bulk pH values between 2 and 12 and was found to act as a cathode. In aerated solutions rotating disk electrode experiments on synthetic Al3Fe electrodes verified that the cathodic reaction corresponded to the reduction of dissolved oxygen. With scanning pH microelectrodes, measurements were carried out near synthetic Al3Fe electrodes which were coupled in a galvanic cell with Al-6061 in NaCl solution. In addition, the pH measured over Al-6061 at a distance of 25-30 mu m from the surface was observed to fluctuate between pH 4 and 8.5 for the first 2 h of immersion in NaCl solutions. Atomic force microscopy images of Al-6061 immersed in buffered aerated 0.6 M NaCl solution (pH 5.5) did not show any evidence of dissolution of the Al around intermetallics. These measurements support the view that Al3Fe particles in Al-6061 serve as local cathodes, that a high pH develops around the intermetallic particles and creates cavities in the host metal, and that interactions among a cluster of intermetallic particles causes a large number of slowly dissolving alkaline cavities to evolve into a small number of rapidly dissolving acidic pits.