The reaction between solid layers to form a product phase has been studied using scanning calorimetry of multilayer Nb/Al and Ni/amorphous‐Si thin films. The most striking feature for both materials systems is the occurrence of two maxima in the reaction rate during the formation of a single product phase, suggesting a two step growth process. A model has been developed in which the first step is taken to be the nucleation and two‐dimensional growth to coalescence of the product phase, in the plane of the initial interface. The second step is taken to be the thickening of the product layer by growth perpendicular to the interface plane. The success of this simple model in describing the principal features of the experimental results on two different materials systems suggests that nucleation is an important aspect of phase formation and selection in these thin‐film reactions.