The bonding and electronic structure of Cu/(0001)Al2O3 and Cu/(1120)Al2O3 interfaces has been studied experimentally using spatially-resolved transmission electron energy loss spectroscopy. The specimen were prepared by depositing Cu on single-crystal α-AI2O3 substrates, which have been Ar+-ion sputter-cleaned prior to the growth of Cu. For both orientations of the α-Al2O3 substrate, atomically abrupt interfaces formed as determined by high-resolution transmission electron microscopy. The investigations of the interfacial Cu-L2,3, Al-L2,3 and 0-K energy loss near-edge structures, which are proportional to the site- and angular-momentum-projected unoccupied density of states above the Fermi level, indicate the existence of metallic Cu-AI bonds at the Cu/AI2O3 interface independent of the substrate orientation. The bonding and electronic structure of Cu / (0001) Al2O3 and Cu / (1120) Al2O3 interfaces has been studied experimentally using spatially-resolved transmission electron energy loss spectroscopy. The specimens were prepared by depositing Cu on single-crystal α-AI2O3 substrates, which have been Ar + -ion sputter-cleaned prior to the growth of Cu. For both orientations of the α-Al2O3 substrate, atomically abrupt interfaces formed as determined by high-resolution transmission electron microscopy. The investigations of the interfacial Cu-L2,3 , Al-L2,3 and 0-K energy loss near-edge structures, which are proportional to the site- and angular-momentum-projected unoccupied density of states above the Fermi level, indicate the existence of metallic Cu-AI bonds at the Cu / AI2O3 interface independent of the substrate orientation.