The behavior of heterointerfaces governs the evolution of microstructures during processing and heat treating, and ultimately controls the resultant morphology of transformation products and therefore the resultant physical and mechanical properties of an engineering material. Atomistic numerical simulation has been proven to be one of the most powerful methods for exploring solid interface behaviors today, especially in the case where they are hardly investigated by experimental techniques, such as atomistic interface migration mechanisms during phase transformations. The micrscpic phase–field model can be used tstudy the microstructure evolution during phase transformations and to trck the migration of an interface at atomic scale at the same time. In this paper, this model was used to investigate the interface migration during the phase transformation from DO₂₂ (Ni₃V) to L1₂ (Ni₃Al) in Ni₇₅Al_xV_25−x(x=4.2, 5.0) alloys. The DO₂₂ phase is precipitated from the disordered fcc phase and then transformed to the L1₂ phase during aging process. Using the simulated microstructures and the occupation probabilities of alloy elements at interfaces, the structure and migration characteristics of ordered domain interfaces formed between DO₂₂ and L1₂ phases are investigated and the mechanism of the phase transformation from DO₂₂ to L1₂ is proposed. The results show that there are five kinds of heterointerface structures to be formed between DO₂₂ and L1₂ phases, four of them are able to migrate during the phase transformation from DO₂₂ to L1₂ except for (002)_D//(001)_L. The structures of (100)_D//(200)_L and (100)_D// (200)_L·1/2[001] themselves are kept unchanged with their migrating, only (002)_D//(002)_L and (002)_D//(002)_L·1/2[100] alternate with each other, and therefore, these two kinds of interfaces appear alternatively. Ni atoms present a site selective behavior during interface migration, they would jump to their nearest neighbor sites and substitute for V atoms with V atoms migrating to the inside of DO22 phases. Al atoms would migrate to interfaces and substitute for Ni or V atoms there. Such a jump and substitution mode of aoms may be an optimization way in thermodynamics and kinetics for interface migration during phase transformaion. All possible atom jump modes inducing the interface migration would obey that the number of jumping atoms during migration must be the least and the jumping distance of atoms the shortest.