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Spinels display promising electrocatalytic ability for oxygen evolution reaction (OER) and organics oxidation reaction because of flexible structure, tunable component, and multifold valence. Unfortunately, limited exposure of active sites, poor electronic conductivity, and low intrinsic ability make the electrocatalytic performance of spinels unsatisfactory. Defect engineering is an effective method to enhance the intrinsic ability of electrocatalysts. Herein, the recent advances in defect spinels for OER and organics electrooxidation are reviewed. The defect types that exist in spinels are first introduced. Then the catalytic mechanism and dynamic evolution of defect spinels during the electrochemical process are summarized in detail. Finally, the challenges of defect spinel electrocatalysts are brought up. This review aims to deepen the understanding about the role and evolution of defects in spinel for electrochemical water/organics oxidation and provide a significant reference for the design of efficient defect spinel electrocatalysts.