The effects of cooling rate and composition on the nucleation and growth kinetics of NiAl, Ni2Al3, and NiAl3 intermetallics were studied for alloys containing 25 and 31.5 ht.% Ni. Fgr the former composition, the peritectic regction Ni Al + Liquid → NiAl3 was studied over cooling rates from 20 to 105 K/s. For the latter composhtion, the reaction NiAl + Liquid → Ni2Al3 was studied at cooling rates ranging form 10 to 600 K/sec. The amounis of constituent phases are shown to depend on the cooling rate, and for the peritectic phases, on the surface area of the primary phase. The nucleation of Ni2Al3 and NiAl3, and the ordering of the aluminum-rich NiAl were also examines uding trans ission electron microscopy. Cooling the NiAl + liquid below the peritectic temperature results in a metastable extension of NiAl with a high dislocation and stacking fault density, followed by the epitaxial nucleation and almost dislocation-free growth of Ni2Al3 In contrast, the nucleation of the NiAl3 on Ni2Al3 occurs directly witgoud the formationof an intermediate region.