The early precipitation process was investigated by the microscopic phase-field kinetic mode. The microscopic morphology evolution, average order parameters and atom occupation probabilities were analyzed. The results show that L10 and L12 phases precipitate form the Ni74.6AlxMo25.4-x alloy first and then L10 phase transforms into L12 phase in the following time. With increasing the aluminum concentration, the atom clustering and ordering process speeds up. Ni atom trends to occupy the αI and αII positions, Al and Mo atoms trend to occupy the β position. With increasing the aluminum concentration, the occupation probabilities of Ni and Al atoms in αI and αII positions increase, the occupation probabilities of Mo atom reduce, the occupation probability of Al atom in β position increases, the occupation probabilities of Ni and Mo atoms reduce.