Strikingly different morphologies of amorphous anodic films on a Mg/40 at.%Ta alloy are shown to result from single-stage and sequential anodizing procedures. The alloy, prepared by magnetron sputtering, was anodized galvanostatically in ammonium pentaborate (pH 8.3) and sodium silicate (pH 12.6) electrolytes at 293 K and studied by transmission electron microscopy, Rutherford backscattering spectroscopy, glow discharge optical emission spectroscopy and X-ray photoelectron spectroscopy. For one-step anodizing in the pentaborate electrolyte, a single-layered film, of approximate composition Ta 2O 5 · MgO, forms at a ratio of ∼1.8 nm V −1. In the silicate electrolyte, an outer, magnesium-rich layer, containing silicon species, also forms, with a ratio of 0.8 nm V −1. The outer layer can develop due to relatively fast migration of magnesium ions in the inner layer and the stabilization of the pH at the film surface, probably linked to generation of a silica gel that also limits loss of magnesium species to the electrolyte. Further thickening of the anodic film, in ammonium pentaborate electrolyte, produces fingers of low resistivity, inner oxide that penetrate the pre-existing, high resistivity outer layer, with a bi-modal distribution of finger sizes. When fingers reach the film surface, magnesium ions are ejected to the electrolyte. The absence of fingers in films grown in sodium silicate electrolyte is possibly due to prevention, by the silica gel, of their initiation.