Nucleation and growth of phases formed during reaction of Ni(V)/Al was described. The growth rate of Al3Ni and Al3Ni2 was estimated with in-situ TEM observations. The Al3Ni phase nucleation front moves parallel to the plane of the films. The solid state diffusion reaction of Ni(V)/Al produces nano-NiAl microstructure. V in Ni(V)/Al forms Al8V5 and restricts coarsening of nanocrystalline NiAl phase.