Phase diagrams, also known as equilibrium phase diagrams, serve as a road map for materials design. However, preparation process of coatings (such as Physical Vapor Deposition, PVD) is generally far from equilibrium and results in metastable phases. Thus, the CALPHAD (Calculation of Phase Diagrams) approach faces a challenge in calculating the metastable phase diagrams for PVD coating materials. Here we summarized the development of the modeling methodology for the metastable phase diagrams, where the model with critical surface diffusion distance established in recent years were highlighted. The CALPHAD approach, first-principles calculations coupled with high-throughput magnetron sputtering experiments were used to model the atomic surface diffusion, while only one key combinatorial experiment was performed to obtain the basic data for the computation, and the calculated metastable phase diagrams were confirmed by further experiments. Therefore, the database of the stable and metastable phase diagrams can be established, which will be used to guide the design of the ceramic coating materials by the relationship of composition, processing, microstructure, and performance. This model can also help to achieve the goal to shorten the time and reduce the costs of materials research and development.