Solvated‐Electron‐Driven Intercalation Enables Electron‐Rich K x NbS 2 Construction and Exfoliation

While creating electron‐rich states can tune material properties, achieving this in van der Waals ( vdW ) materials lacking cationic frameworks remains challenging. Here, we report a molten‐salt solvated‐electron strategy that injects electrons into the vdW gaps of transition metal dichalcogenides (TMDCs). Using a Ga‐KCl system, we construct an electron‐rich intermediate K x NbS 2 ( x ≤0.5), wherein coupled K + intercalation provides charge compensation and drives superlattice formation. Spectroscopic characterization confirm electron injection and partial reduction of the host lattice. This state enables solvent‐dependent exfoliation, protic solvents drive a chemical pathway, whereas aprotic solvents facilitate physical delamination via electrostatic repulsion. Demonstrating applicability across TMDCs (NbS 2 , TaS 2 , NbSe 2 and WS 2 ), alkali salts, and electron donors, this strategy provides a route to engineer the electronic structures and interlayer interactions of two‐dimensional (2D) materials for catalysis and quantum applications.