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Engineering electronic bandgaps is crucial for applications in information technology, sensing, and renewable energy. Transition metal dichalcogenides (TMDCs) offer a versatile platform for bandgap modulation through alloying, doping, and heterostructure formation. Here, the synthesis of a 2D Mo_xW_1‐xS₂graded alloy is reported, featuring a Mo‐rich center that transitions to W‐rich edges, achieving a tunable bandgap of 1.85 to 1.95 eV when moving from the center to the edge of the flake. Aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy showed the presence of sulfur monovacancy, V_S, whose concentration varied across the graded Mo_xW_1‐xS₂layer as a function of Mo content with the highest value in the Mo‐rich center region. Optical spectroscopy measurements supported by ab initio calculations reveal a doublet electronic state of V_S, which is split due to the spin‐orbit interaction, with energy levels close to the conduction band or deep in the bandgap depending on whether the vacancy is surrounded by W atoms or Mo atoms. This unique electronic configuration of V_Sin the alloy gave rise to four spin‐allowed optical transitions between the V_Slevels and the valence bands. The study demonstrates the potential of defect and optical engineering in 2D monolayers for advanced device applications.

The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)‐grown monolayer WS₂, it is found that a higher density of transition metal dopants is always incorporated in sulfur‐terminated domains when compared to tungsten‐terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron‐ and vanadium‐doped WS₂monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge‐dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten‐zigzag edges, resulting in the formation of open sites at sulfur‐zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in‐plane hetero‐/multi‐junctions that display fascinating electronic, optoelectronic, and magnetic properties.