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Single‐atom catalysts (SACs) have attracted extensive interest to catalyze the oxygen reduction reaction (ORR) in fuel cells and metal–air batteries. However, the development of SACs with high selectivity and long‐term stability is a great challenge. In this work, carbon vacancy modified Fe–N–C SACs (FeH–N–C) are practically designed and synthesized through microenvironment modulation, achieving high‐efficient utilization of active sites and optimization of electronic structures. The FeH–N–C catalyst exhibits a half‐wave potential (E1/2) of 0.91 V and sufficient durability of 100 000 voltage cycles with 29 mV E1/2 loss. Density functional theory (DFT) calculations confirm that the vacancies around metal–N4 sites can reduce the adsorption free energy of OH*, and hinder the dissolution of metal center, significantly enhancing the ORR kinetics and stability. Accordingly, FeH–N–C SACs presented a high‐power density and long‐term stability over 1200 h in rechargeable zinc–air batteries (ZABs). This work will not only guide for developing highly active and stable SACs through rational modulation of metal–N4 sites, but also provide an insight into the optimization of the electronic structure to boost electrocatalytical performances.

Cathodes in lithium‐ion batteries with anionic redox can deliver extraordinarily high specific capacities but also present many issues such as oxygen release, voltage hysteresis, and sluggish kinetics. Identifying problems and developing solutions for these materials are vital for creating high‐energy lithium‐ion batteries. Herein, the electrochemical and structural monitoring is conducted on lithium‐rich cathodes to directly probe the formation processes of larger voltage hysteresis. These results indicate that the charge‐compensation properties, structural evolution, and transition metal (TM) ions migration vary from oxidation to reduction process. This leads to huge differences in charge and discharge voltage profile. Meanwhile, the anionic redox processes display a slow kinetics process with large hysteresis (≈0.5 V), compared to fast cationic redox processes without any hysteresis. More importantly, a simple yet effective strategy has been proposed where fine‐modulating local oxygen environment by the lithium/oxygen (Li/O) ratio tunes the anionic redox chemistry. This effectively improves its electrochemical properties, including the operating voltage and kinetics. This is also verified by theoretical calculations that adjusting anionic redox chemistry by the Li/O ratio shifts the TM 3d—O 2p bands and the non‐bonding O 2p band to a lower energy level, resulting in a higher redox reaction potential.

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