The structure of rapidly solidified Al-Si-based alloys and its relationship to subsequent anodic film growth in near neutral and acid solutions have been investigated. Solidification of the alloys proceeds via pre-dendritic nuclei, associated with rugosity of the casting surface, from which cellular-type growth, comprised of aluminium-rich material surrounded by silicon-containing material, emanates. Observation of ultramicrotomed sections of the alloys and their anodic films reveals the local oxidation of the silicon-rich phase and its incorporation into the anodic alumina film, formed in near neutral solutions. Such incorporation occurs but resultant isolation of the silicon-rich phase is not possible for anodizing in phosphoric acid, and a three-dimensional network of the oxidized silicon-containing phase, with continuing development of porous anodic alumina, is observed.