In this study, a generalized guideline is identified to predict the interaction between two‐dimensional (2D) layered materials and substrate surfaces. Additionally, the van der Waals (vdW) heterostructures commensurability, the phase formation and the strain relaxation are identified during interface growth. To achieve such a general overview, the case of Ge‐Sb‐Te (GST) alloys on InAs(111) is studied. In this system, low‐lattice mismatch conditions are fulfilled to avoid relaxation due to formation of misfit dislocations and allow to correctly identify vdW epitaxy. At the same time, the substrate can be efficiently prepared into self‐ and un‐passivated surfaces to clarify the role of the surface interaction. Furthermore, the GST epilayer exhibits two different highly ordered 2D structures and a three‐dimensional disordered structure, allowing to directly infer the nature of the epitaxy. This study opens the way for the design and …