Ni/Al multilayer films with pair thicknesses of 10 and 20 nm and with overall compositions in the range 48–88 at. % Al were prepared by sputtering. For comparison, Ni‐Al alloy films in the same concentration range were prepared by co‐deposition of the elements. The films were studied by x‐ray diffraction, electron diffraction, and differential scanning calorimetry. It was found that the B2 NiAl phase with a metastable concentration of approximately 63 at. % Al was the first phase to grow upon annealing of the multilayer films. The growth of this phase could be described by Johnson–Mehl–Avrami kinetics with an activation energy of 0.8 eV and an Avrami exponent of 0.5. This low activation energy was consistent with the observation that the phase had formed during deposition and continued to grow upon annealing at low temperatures to thicknesses of a few nanometers. If the reactant phases were not fully consumed by the B2 phase growth, the subsequent reaction was the formation of NiAl3, previously thought to be the first product phase in the Ni‐Al system. The reduction of driving force by the preceding B2 phase growth explains why the formation of NiAl3takes place by a nucleation‐and‐growth process, an observation that has been discussed controversially in the recent literature. The nucleation and growth of NiAl3had an activation energy of 1.5 eV in agreement with previous studies. ©1996 American Institute of Physics.