The reduction of nickel oxide and the formation of AlNi intermetalic phase at 1200°C for 2.5 till 10 min interval, during the aluminothermic method were studied, simultaneously. Aluminium was used as a reduction agent of nickel oxide in molten cryolite (Na3AlF6). The changes in the amount of Ni in primitive metal samples were determined by atomic absorption analysis at different times. The achieved microstructure in quenched samples was observed by SEM. The prepared phases were recognised by XRD and EDS analysis. The results revealed that samples were combination of AlNi, Al3Ni2, Al3Ni and Al in the absence of Ni, NiO and Al2O3 phases. The increasing of time causes the higher amount of AlNi phase to a continuous network.