Although two-dimensional (2D) atomic layers, such as transition-metal chalcogenides, have been widely synthesized using techniques such as exfoliation1,2,3 and vapour-phase growth4,5, it is still challenging to obtain phase-controlled 2D structures6,7,8. Here we demonstrate an effective synthesis strategy via the progressive transformation of non-van der Waals (non-vdW) solids to 2D vdW transition-metal chalcogenide layers with identified 2H (trigonal prismatic)/1T (octahedral) phases. The transformation, achieved by exposing non-vdW solids to chalcogen vapours, can be controlled using the enthalpies and vapour pressures of the reaction products. Heteroatom-substituted (such as yttrium and phosphorus) transition-metal chalcogenides can also be synthesized in this way, thus enabling a generic synthesis approach to engineering phase-selected 2D transition-metal chalcogenide structures with good stability at high temperatures (up to 1,373 kelvin) and achieving high-throughput production of monolayers. We anticipate that these 2D transition-metal chalcogenides will have broad applications for electronics, catalysis and energy storage.