Abstract: A micron-thick nickle layer on pure aluminum foils was obtained by electroless nickel plating. The nickel plated aluminum foils were stacked, hot pressed and accumulative rolling bonded (1-7 passes) to prepare Ni/Al multilayer laminates. The microstructure and exothermic properties of the multilayer laminates were investigated. The results show that the electroless nickel plated layer was amorphous and crystallized during the subsequent hot pressing process. With the increase of the accumulative rolling pass, the nickel layer gradually necked and fractured. The nickel fragments were embedded in the aluminum, increasing the contact area between nickel and aluminum, leading to an increase of the exothermic properties of the Ni/Al multilayer laminates; the energy density of the laminates increased from 520.27 J·g^-1 with 1 pass to 1 203.4 J·g^-1 with 7 passes, which was 87.15% of the theoretical value. The initial reaction temperatures of the Ni/Al multilayer laminates accumulative rolling bonded with different passes were all higher than 475℃, indicating that the multilayer laminates had good stability at room temperature.