By using molecular dynamics method with the second nearest neighbor modified embedded-atom method (2NN MEAM) interatomic potential, we studied the γ/θ-DO₂₂ interfacial structure of Ni-Al-V superalloy at different compositions, and calculated the interfacial energy and the work of separation on the interfaces. The research shows that with the Al atom concentration increases, the interfacial energy can increase while the work of separation can reduce; with the concentration of V atoms increases, the interfacial energy increases first and then decreases; but the change of atomic concentration has little effect at the work of separation; and the interfacial energy and the work of separation are closely related to the interfacial migration. It has great guiding significance to the alloy design that the results can be used to further study the dynamic behavior of Ni-Al-V superalloys in the process of precipitation, such as the composition segregation and interfacial migration.