Comprehensive SummaryThe electrochemical processes of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) play a crucial role in various energy storage and conversion systems. However, the inherently slow kinetics of reversible oxygen reactions present an urgent demand for the development of efficient oxygen electrocatalysts. Recently, metal‐organic framework (MOF) derivatives have attracted extensive attention in electrocatalysis research due to their unique porous structure, abundant active sites, and tunable structural properties. Especially, the optimization of the electronic structure of active sites in MOF derivatives has been proven as an effective strategy to enhance the catalytic activity. In this review, we provide an overview of the electronic structure optimization strategies for active sites in MOF derivatives as advanced catalysts in various O—O bond activation reactions, including the construction of synergistic effects between multiple sites, the development of heterogeneous interfaces, the utilization of metal support interactions, and the precise modulation of organic ligands surrounding catalytic active sites at the atomic level. Furthermore, this review offers theoretical insights into the oxygen activation and catalytic mechanisms of MOF derivatives, as well as the identification of active sites. Finally, the potential challenges and prospects of MOF derivatives in electrocatalysis are discussed. This review contributes to the understanding and advancement of efficient oxygen electrocatalysis in energy systems. Key Scientists