Zi‐Tian Lei, Wen‐Gang Cui, Yang Zhang, Ke Wang, Fan Gao, Zichao Shen, Jindou Shi, Yuanchao Yang, Xinqiang Wang, Dingsheng Wang, H. Y. Pan
ABSTRACT Electrocatalysis is central to sustainable energy conversion and industrial electrosynthesis, yet its efficiency and selectivity are profoundly governed by the dynamic interfacial microenvironment, particularly the hydrogen‐bond networks (HBNs) formed among catalysts, electrolytes, and intermediates. Unlike isolated hydrogen bonds, interfacial HBNs exhibit unique characteristics, such as connectivity, synergy, and time variability, which collectively regulate reaction kinetics and pathways. This review systematically summarizes recent advances in understanding and dynamically regulating interfacial HBNs, with a focus on their core functionalities: enabling ultrafast proton conduction via the Grotthuss mechanism, stabilizing key reaction intermediates to steer selectivity, and modulating interfacial water configuration for optimized reactant accessibility. To harness these functionalities, dynamic regulation strategies are detailed, including catalyst surface engineering (surface functional group grafting, single‐atom site engineering, and interface architecture designing), and electrolyte engineering (ions, solvents), and highlight how state‐of‐the‐art characterization techniques (e.g., in situ surface‐enhanced infrared absorption spectroscopy, correlated vibration spectroscopy, scanning probe microscopy etc.) are decoding HBNs dynamics at the molecular level. Finally, this study outlines current challenges in real‐time tracking, atomic‐scale and ultrafast dynamic characterization, and multi‐factor decoupling, and propose future directions including AI‐aided network design and smart electrolyte development, advocating for a HBNs centric paradigm to guide the design of next‐generation electrocatalysts.