Phase-field modeling coupled with calculation of phase diagram (CALPHAD) database was utilized to perform a series of two-dimensional phase-field simulations of microstructure evolution in the γ + γ′/γ + γ′ Ni–Al–Cr mode bond coat/substrate systems. With the aid of phase-field simulated microstructure evolution, the relationship between the interdiffusion microstructure and the cohesiveness/aluminum protective property with different alloy compositions and bond coat thicknesses was fully discussed. A semi-quantitative tie-line selection criteria for alloy composition of the bond coat/substrate system with the identical elements, i.e., that the equilibrium Al concentrations of γ′ and γ phases in the bond coat should be similar to those in substrate, while the phase fraction of γ′ in the bond coat tends to be higher than that in the substrate, was then proposed to reduce the formation of polycrystalline structure and thermal shock from the temperature gradient.