<p>Interfacial water structure critically affects the hydrogen evolution reaction (HER) in neutral and alkaline media, where sluggish water dissociation limits the Volmer step. Here, we report a distance-programmed metal-organic layer (MOLs) that is laid directly on metal electrode surfaces to regulate the near-surface microenvironment in HER. The vertical separation between the Hf₆(<i>μ</i>₃-O)₄(<i>μ</i>₃-OH)₄ building units of the MOLs and the underlying metal surface can be systematically tuned by post-synthetic ligand exchange on the MOLs surface. Under operating conditions, deprotonation of <i>μ</i>₃-OH on the Hf₆(<i>μ</i>₃-O)₄(<i>μ</i>₃-OH)₄ cluster generates arrays of <i>μ</i>₃-O⁻ groups that can electrostatically enrich hydrated alkali cations at the metal-electrolyte interface. <i>In situ</i> Infrared spectroscopy showed that interfacial water reorganized after MOLs loading, from strongly hydrogen-bonded networks toward weakly bound, H-down configurations favorable for O–H bond cleavage. Shorter MOLs-metal distances markedly amplify this effect, leading to accelerated hydrogen evolution kinetics. On Pt electrodes, optimized spacing reduces the overpotential at 10 mA cm⁻² by over 100 mV relative to bare metal. The enhancement persists across a broad pH range (3–9) and generalizes across multiple metal substrates, including Cu, Au, W, Co, and Ni. These results establish surface-laid, distance-defined MOLs as an interesting tool to study interfacial water structure and electrochemical kinetics through spatially programmed electrostatics.</p>