Abstract
Electrochemical water splitting represents a cornerstone technology for sustainable hydrogen production, yet its practical application remains constrained by the sluggish kinetics of the oxygen evolution reaction (OER) and reliance on noble‐metal‐based electrocatalysts. Developing bifunctional catalysts capable of simultaneously promoting the hydrogen evolution reaction (HER) and OER within a unified platform offers a streamlined approach to reducing system complexity and material cost. Metal–organic frameworks (MOFs), renowned for their high surface area, tunable porosity, and structural versatility, have emerged as transformative precursors for advanced electrocatalyst design. Upon thermal or chemical conversion, MOFs give rise to nanostructured, conductive materials featuring hierarchical architectures, multi‐metallic active sites, and engineered defect domains. This review systematically presents recent progress in MOF‐derived bifunctional electrocatalysts for overall water splitting, beginning with synthetic strategies and structural engineering principles. The discussion then addresses electronic structure modulation and structure–activity correlations, emphasizing synergistic charge transport and morphological control. Key challenges, including durability under operational conditions, scalability of synthesis, and mechanistic elucidation, are critically assessed. The review concludes by outlining future research directions toward rationally designing MOF‐based electrocatalysts that enable efficient, stable, and scalable hydrogen production for next‐generation renewable energy systems.