Interfacial atomic and electronic structures of Cu/Al2O3(0001) and Cu/Al2O3(1120) prepared by a pulsed-laser deposition technique were characterized by high-resolution transmission electron microscopy (HRTEM) and electron energy-loss spectroscopy (EELS). It was found that both systems have O-terminated interfaces, irrespective of different substrate orientations. This indicates that Cu-O interactions across the interface play an important role for the Cu/Al2O3 Systems.