Abstract The effect of tungsten species on the incorporation and migration of phosphorus species within anodic alumina is investigated. The study employs barrier anodic films, formed on a sputtering‐deposited Al‐15at.%W alloy in phosphate electrolytes. The films consist of either an outer tungsten‐containing region and an inner tungsten‐free region, or a tungsten‐containing region only. Phosphorus species are shown to migrate inward in the tungsten‐containing alumina more slowly than in the tungsten‐free alumina. In contrast, the outward migration of tungsten species is relatively unaffected by the presence of phosphorus species. The relevance of the results to the use of tungsten tracers for the study of porous film growth is discussed. Copyright © 2010 John Wiley & Sons, Ltd.