The electrocatalytic performance of metal–nitrogen–carbon (M─N─C) single‐atom catalysts remains a significant challenge due to their rigid active center. Controllable tuning of the local microenvironment and electronic structure is critical for M─N─C single‐metal site catalysts in improving the electrochemical performance and exploring the reaction mechanism. Herein, Co─N₄ is selected as a benchmark among various M─N─C catalysts based on theoretical prediction and experimental studies. A dual‐metal S─Fe─Co─N₅ catalyst is constructed by embedding Fe and S into the structure of Co─N₄ motifs. Theoretical analysis and in situ characterizations illustrate that the active sites will in situ combine an O‐axial ligand to form S─Fe─Co─N₅─O structure during the oxygen evolution reaction (OER), which can reduce the reaction energy of O^*→OOH^*. The Ab Initio Molecular Dynamics simulations and deformation energy for H^*/O^* adsorption reveal that the Fe─Co and S─Fe bonds exhibit flexible characteristics compared to the Co/Fe─N bonds. This flexibility of S─Fe─Co─N₅─O structure facilitates the OER performance by reducing the OOH^*→O₂, which is the OER rate‐determining step, resulting in superior performance. The optimized S─Fe─Co─N₅─O catalyst exhibits excellent OER (260 mV@50 mA cm⁻²) and hydrogen evolution reaction (138 mV@10 mA cm⁻²) performance in alkaline electrolytes. The reported regulation strategy ameliorates the micro‐environment of Co─N₄ with tunable flexibility, which helps allow a basic comprehension of the electrochemical reaction mechanism.

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