In order to understand the anodic behaviour of Al-Mo and Al-W amorphous alloys in the berate buffer electrolyte, samples of these alloys were polarized galvanostatically. The resultant anodic films were thicker than the passive films formed during potentiodynamic polarization enabling detailed examination of the films and alloy substrates by surface analytical methods. AES investigations suggest that the anodic films formed at low and moderate voltages on Al-Mo or Al-W amorphous alloys consist of ill-oxide, whereas refractory metals remain unoxidized and enriched at the film/substrate interface. Molybdenum and tungsten act as 'dissolution moderators', restraining the substrate dissolution process at the film/substrate interface. However, after anodization at high voltages (50 V), AES revealed the presence of an oxidized refractory metal in the inner part of the anodic film. Based on these results of growth of thick anodic films, the role of Mo and W in enhancing the pitting corrosion resistance is discussed. (C) 1999 Elsevier Science S.A. All rights reserved.