Self‐propagating explosive reactions, with a reaction front speed of about 4 m/s, have been observed in free‐standing polycrystalline Al/Ni multilayer thin films. The resultant phases and microstructures are compared with those obtained by conventional thermal annealing. We show evidence which indicates that melting occurred in the explosive reactions of films with an atomic concentration ratio of 3Al:1Ni. It is also observed that the propensity of multilayer films to undergo explosive reactions is dependent on the modulation length of the film as well as on the ambient temperature. These observations are interpreted with a simple model based on the rate balance between the rates of heat generation and heat dissipation.