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 NiAl3 and Ni2Al3 during solidification. After annealed, Ni2Al3 and NiAl3 still exist in the joints of the couples. The reasons for the formation of Ni2Al3 and NiAl3, as well as the absence of NiAl, Ni5Al3 and Ni3Al 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 NiAl3 and Ni2Al3 phases were also calculated according to the Arrhenius equation. 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 NiAl3 and Ni2Al3 during solidification. After annealed, Ni2Al3 and NiAl3 still exist in the joints of the couples. The reasons for the formation of Ni2Al3 and NiAl3, as well as the absence of NiAl, Ni5Al3 and Ni3Al 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 NiAl3 and Ni2Al3 phases were also calculated according to the Arrhenius equation.