We employ density functional calculations to present a detailed picture of the atomic-level interactions at doped Al2O3/Ni interfaces. In Particular, we emphasize the importance of local structural and electronic relaxation in determining the global adhesion between metal/ceramic couples. We find localized metal-metal and dopant metal-oxo bonding can produce strong interface adhesion even where no new interfacial reaction product is formed, driven by a combination of oxide donation to dopant acceptor orbitals along with localized covalent dopant metal-oxo and several types of metal-metal bonds. Understanding the local mechanisms of strengthening heterogeneous interfaces may result in practical advances ranging from coating to catalytic applications.