Aluminum powders are known to provide outstanding volumetric exothermic enthalpy energy during thermal oxidation. However, the amount of energy released tends to be limited by the dense surface oxide (Al2O3) layer of the powder. Hence, a prerequisite for improving the reactivity of passivated Al particles is to remove the Al2O3 film from the surface. Considering that the self-propagating high-temperature synthesis (SHS) reaction of Ni and Al can generate additional exothermic heat in Al powder, Ni can be considered as a promising alternative to the surface oxide layer. Here, we report oxide-layer-free fine Al particles with a characteristic Ni/Al interface, where a Ni layer replaces the Al2O3 film. The microstructure of the synthesized powder consists of a 200-nm-thick Ni layer homogeneously coated on the Al surface, which has nanosized craters caused by the geometrical removal of Al2O3. Thermal analysis and in-situ heating transmission electron microscopy (TEM) results clearly show that active interdiffusion of atoms through the Ni/Al interface results in the formation of intermetallic compounds to provide additional exothermic energy, compared to the result for simply mixing Ni and Al powders. Hence, these findings provide new routes for the design and application of reactive metallic particles using the SHS reaction.