We have observed the formation of the hydrotalcite-like phase of lithium dialuminate, LiAl2(OH)6OH · 2H2O, and also the carbonate analog, by the oxidation of aluminum sheet and also aluminum powder in aqueous lithium hydroxide or lithium carbonate solutions. A secondary phase, bayerite, was also observed following the oxidation process, except when the aluminum was treated with lithium oxalate solutions where it is the principal phase. Results have been obtained for the time required to form a passivating film to hydrogen formation as a function of temperature and oxidizing solution. Grazing incidence x-ray diffraction of aluminum sheet samples, combined with polycrystalline x-ray diffraction on similarly treated aluminum powder, were used to evaluate the formation of the films. Both transmission and reflectance infrared absorption spectra on powder and sheet samples were used to support the x-ray observations. Scanning and transmission electron microscopies show morphological differences between preparations, film thicknesses of 10–20 μm, and also film defects. Additional SIMS analysis determined the relative lithium and aluminum concentrations in the films, suggesting that a higher concentration of lithium occurs when lithium carbonate is present in the reacting solutions.