The interfacial chemistry between Ni and Al2O3 has been studied during the initial stages of bonding. We have evaporated thin films of Ni on different alumina substrates (thin oxide film on metallic Al, polished and scratched sapphire crystals, surface with second phase precipitates) and have analyzed how the interface grows, in situ, using X-ray Photoelectron Spectroscopy. It was found that a certain fraction of the first monolayer of Ni which forms on the alumina surface undergoes charge transfer to form NiO. This is due to oxygen-active sites such as unattached oxygen bonds on the surface. A measure of the concentration of such sites can therefore be obtained from the submonolayer fraction of Ni that gets oxidized. It was found that a rough surface offered less oxidation sites for Ni than a smooth one whereas a surface with second phase MgAI2O4 (spinel) precipitates offered more oxidation sites. Also, there is much less oxidation on a thin film of amorphous alumina grown on metallic Al than on a polished bulk sapphire surface. The implications of these studies to further understanding of the metal-ceramic interface have been discussed.