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Controlled synthesis of metastable materials away from equilibrium is of interest in materials chemistry. Thin-film deposition methods with rapid condensation of vapour precursors can readily synthesize metastable phases but often struggle to yield the thermodynamic ground state. Growing thermodynamically stable structures using kinetically limited synthesis methods is important for practical applications in electronics and energy conversion. Here, in this study, we reveal a synthesis pathway to thermodynamically stable, ordered layered ternary nitride materials, and discuss why disordered metastable intermediate phases tend to form. We show that starting from elemental vapour precursors leads to a 3D long-range-disordered MgMoN₂ thin-film metastable intermediatemore » structure, with a layered short-range order that has a low-energy transformation barrier to the layered 2D-like stable structure. This synthesis approach is extended to ScTaN₂, MgWN₂ and MgTa₂N₃, and may lead to the synthesis of other layered nitride thin films with unique semiconducting and quantum properties.« less