The anodizing behaviour of sputter-deposited Al-4 at.% Au-1 at.% Cu and Al-1.6 at.% W-0.6 at.% Zn alloys has been examined by Rutherford backscattering spectroscopy and transmission electron microscopy. Initially, a uniform, amorphous alumina film, free of copper and gold species, is formed on the Al-Au-Cu alloy; at the same time, a thin alloy layer, beneath the anodic film, is enriched in copper and gold. The uniform film growth is eventually terminated by generation of oxygen at gold-rich particles at, or near, the alloy/film interface, leading to bubble formation, subsequent rupture of the film and release of oxygen. Film growth on the Al-W-Zn alloy causes mainly enrichment of tungsten in the alloy, with the limited enrichment of zinc contrasting with the behaviour of Al-Zn alloys. Uniform film growth proceeds to high voltages with incorporation of mobile tungsten and zinc species into the film.