The controlled formation of a functional adlayer at the catalyst-water interface is a highly challenging yet potentially powerful strategy to accelerate proton transfer and deprotonation for ultimately improving the performance of proton-exchange membrane water electrolysis (PEMWE). In this study, the synthesis of robust vinylene-linked covalent organic frameworks (COFs) possessing high proton conductivities is reported, which are subsequently hybridized with ruthenium dioxide yielding high-performance anodic catalysts for the acidic oxygen evolution reaction (OER). In situ spectroscopic measurements corroborated by theoretical calculations reveal that the assembled hydrogen bonds formed between COFs and adsorbed oxo-intermediates effectively orient interfacial water molecules, stabilizing the transition states for intermediate formation of OER. This determines a decrease in the energy barriers of proton transfer and deprotonation, resulting in exceptional acidic OER performance. When integrated into a PEMWE device, the system achieves a record current density of 1.0 A cm