A novel method for preparing aluminum/aluminum nitride ceramics (Al/AlN) substrates is proposed in this paper. The method included two processes: (1) the surface of AlN was coated with a CuO thick film and sintered; (2) Al foil was put on the pretreated (in process 1) AlN surface and bonded to AlN through pre-heating at 400 °C and final heating at 660 °C in N2-H2 reduction atmosphere. The experimental results obtained by optical and scanning electron microscope (SEM) observations as well as by X-ray diffraction analysis at the cross-sections of the joints and the fracture surfaces, suggest that the reaction mechanism starts with the reaction of CuO with AlN to form CuAlO2, when the AlN coated with CuO is heat-treated at high temperature. A Cu layer is produced by the reduction of CuO and Cu diffuses in the Al foil, forming strong Al/AlN joints. Elongated crystals of Al2Cu are developed in the reaction zone at the interface between Al and AlN. The results of mechanical tests showed that the peeling-off strength of the Al foil from the surface of the AlN substrate reached a value of 15.4 MPa for the Al/AlN couples produced after 30 min of heat treatment at 660 °C.