The differences in the electrochemical behavior of a rapidly solidified, two-phase (matrix and dispersoid) Al-based alloy containing Fe, V, and Si (FVS0812 alloy) and the bulk form of its matrix and dispersoid phases were investigated in sulfuric acid. FVS0812 exhibited generally higher electrochemical activity than the matrix material due to the presence of the very active dispersoid phase in the alloy. Impedance studies indicated that the properties of thin films formed on the FVS0812 and matrix substrates during only 5 min of anodization are similar, whereas the film formed on the alloy during 2.5 h of anodization was substantially less resistive and contained a thinner and/or damaged underlying barrier oxide compared to a comparable film formed on the matrix. Compared to the classical structure of porous Al oxide films with underlying barrier oxide, the oxide film on FVS0812, as seen by TEM, was thinner, with an intermittent barrier oxide underlying a porous oxide of contorted morphology. Evidence is seen for the loss of dispersoids from the oxide film, leaving voids throughout its structure, perhaps the reason for its lack, of physical adherence and its limiting thickness.