Oxygen Spillover: Revolutionizing Catalytic Performance and Disrupting Mechanistic Paradigms in Sustainable Chemistry

Abstract Oxygen spillover, a dynamic interfacial phenomenon in catalysis, enables the migration of active oxygen species (*O, *OH) across catalyst interfaces, overcoming the limitations of traditional static active sites and establishing a new paradigm for optimizing catalytic performance in sustainable chemistry. This review systematically examines mechanistic advances in oxygen spillover and its applications in energy‐related catalytic reactions (e.g., oxygen evolution reactions, oxygen reduction reactions, hydrogen evolution reactions, hydrogen oxidation reactions, organics oxidation reactions), highlighting its core advantage in decoupling intermediate adsorption/desorption energetics and reconstructing reaction kinetic pathways. By integrating in situ characterization and theoretical simulations, the regulatory mechanisms of electronic structure gradients, defect engineering, and heterojunction design on spillover kinetics are elucidated, along with rational design strategies for atomically precise catalysts. The oxygen spillover mechanism not only addresses the trilemma of catalytic efficiency‐selectivity‐stability but also provides unified design principles for cross‐disciplinary catalytic systems, driving the paradigm shift in catalysis science from phenomenological description to predictive design.