AbstractThe electronic properties of two-dimensional semiconductors can be strongly modulated by interfacing them with atomically precise self-assembled molecular lattices, yielding hybrid van der Waals heterostructures (vdWHs). While proof-of-concepts exploited molecular assemblies held together by lateral unspecific van der Waals interactions, the use of 2D supramolecular networks relying on specific non-covalent forces is still unexplored. Herein, prototypical hydrogen-bonded 2D networks of cyanuric acid (CA) and melamine (M) are self-assembled onto MoS₂ and WSe₂ forming hybrid organic/inorganic vdWHs. The charge carrier density of monolayer MoS₂ exhibits an exponential increase with the decreasing area occupied by the CA·M unit cell, in a cooperatively amplified process, reaching 2.7 × 10¹³ cm⁻² and thereby demonstrating strong n-doping. When the 2D CA·M network is used as buffer layer, a stark enhancement in the catalytic activity of monolayer MoS₂ for hydrogen evolution reactions is observed, outperforming the platinum (Pt) catalyst via gate modulation.