First principles density functional calculations are used to study the structure and properties of ultrathin films of alumina on Al(111) and Ru(0001) substrates. We focus on ∼5 Å two O-layer films, naturally produced by oxidizing NiAl, Ni3Al, and Al deposited on Ru(0001). The interface consists of chemisorbed l×1 oxygen on the underlying metal [1], with a nearly coplanar layer of Al2O3 above. The lowest energy structure of the Al-sublattice is found to consist of zig-zag rows of octahedral and tetrahedral Al ions, resembling the bulk κ-phase. Eleven different adsorbed metals, spanning the periodic table, have been studied [2]. At low coverage the bond is purely ionic; at high coverage most metals bind principally by polarization. Contrary to speculations, isolated vacancies are found on MgO(100) not to directly promote metal nucleation [3], and we suggest this behavior is general. However, ad-OH is found not only to promote island nucleation, but can also, in high concentrations, produce wetting of alumina by Cu [4].