Formation and growth of the intermediate phases in the Ni-Al diffusion couples prepared by pouring technique were investigated. Electron probe microanalysis, scanning electron microscopy and X-ray diffraction were used to characterize the product phases in the joints. The results show that two intermediate phases form in the sequence of NiAl 3 and Ni 2 Al 3 during solidification. After annealed, Ni 2 Al 3 and NiAl 3 still exist in the joints of the couples. The reasons for the formation of Ni 2 Al 3 and NiAl 3 , as well as the absence of NiAl, Ni 5 Al 3 and Ni 3 Al were discussed, respectively. The growth kinetics of both product phase layers indicates that their growth obeys the parabolic rate law. The activation energies and frequency factors for NiAl 3 and Ni 2 Al 3 phases were also calculated according to the Arrhenius equation.