Stochastically structured Ni/Al reactive nanocomposites (RNCs) were prepared using short-term high-energy ball milling. Several milling times were utilized to prepare RNCs with differing internal nanostructures. These internal structures were quantitatively and statistically analyzed by use of serial focused ion beam sectioning coupled with 3D reconstruction techniques. The reaction kinetics were analyzed using the electrothermal explosion technique for each milling condition. It is shown that the effective activation energy (Eef) ranges from 79 to 137 kJ/mol and is directly related to the surface area contact between the reactants. Essentially, the reaction kinetics can be accurately controlled through mechanical processing techniques. Finally, the nature of the reaction is considered; the mechanistic effect of the reactive and three diffusive activation energies on the effective activation energy is examined.