Laser Raman spectroscopy has been applied under in situ and ex situ conditions to the anodic oxide films formed on titanium at various potentials in neutral phosphate and acidic sulfate solutions. The Raman spectra reveal that the anodic oxide film is primarily composed of an anatase type of . From the relation between the Raman band intensity, film thickness, and surface morphology, it is likely that the film changes from the amorphous state to the crystalline state beyond a certain critical potential.