The microscopic structure and evolution of ordered interphase boundary of Ni-Al-V alloy was investigated using microscopic phase-field model. The results show that three kinds of interphase boundaries are formed between LI2 phases, the width of the interphase boundaries are narrower, and of which one kind of interphase boundary is in equilibrium for the occupation probability of Al atoms. According to the different orientation variants of [ 10] and [01 ] of the projection of D022, there form eight kinds of interphase boundaries structure, in which the interphase boundaries are wider with the same orientation variants, and the occupation probability of V atoms reach the equilibrium value with different orientation variants. There are four kinds of interphase boundaries between the different phases. The occupation probability of atoms in the interphase boundaries reach the equilibrium value and two phase transit continuously, for one phase precipitate from the interphase boundary of another. With the precipitation process, the interphase boundaries formed in [01] direction of D022 transform from disordered to ordered and become narrower firstly and then dissolve into disordered phase.