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Developing high‐performance oxygen evolution reaction (OER) catalysts are critical for the practical application of many electrochemical energy devices. In this study, taking layered perovskite oxide thin films as the model system, it is demonstrated that the OER pathway can be effectively shifted by activating lattice oxygen, leading to strongly enhanced intrinsic activity. The OER performance of Ruddlesden‐Popper (RP)‐phase cobaltite is significantly enhanced as Sr doping at the A site increases, which is attributed to the shift of the reaction pathway from adsorbate evolution mechanism (AEM) to lattice oxygen‐mediated mechanism (LOM). Advanced spectroscopic techniques and density functional theory calculations reveal that the Sr dopant effectively facilitates oxygen ligand hole formation, charge transfer from the oxygen sites, and the formation and migration of oxygen vacancy, hence promoting lattice oxygen to participate in surface reactions. The results provide critical insight into the role of oxygen activity and offer a potential way for constructing highly active electrocatalysts. [ABSTRACT FROM AUTHOR]

Doping perovskite oxide with different cations is used to improve its electro‐catalytic performance for various energy and environment devices. In this work, an activated lattice oxygen activity in Pr0.4Sr0.6CoxFe0.9−xNb0.1O3−δ (PSCxFN, x = 0, 0.2, 0.7) thin film model system by B‐site cation doping is reported. As Co doping level increases, PSCxFN thin films exhibit higher concentration of oxygen vacancies (Vo••) as revealed by X‐ray diffraction and synchrotron‐based X‐ray photoelectron spectroscopy. Density functional theory calculation results suggest that Co doping leads to more distortion in FeO octahedra and weaker metaloxygen bonds caused by the increase of antibonding state, thereby lowering Vo•• formation energy. As a consequence, PSCxFN thin film with higher Co‐doping level presents larger amount of exsolved particles on the surface. Both the facilitated Vo•• formation and B‐site cation exsolution lead to the enhanced hydrogen oxidation reaction (HOR) activity. Excessive Co doping until 70%, nevertheless, results in partial decomposition of thin film and degrades the stability. Pr0.4Sr0.6(Co0.2Fe0.7Nb0.1)O3 with moderate Co doping level displays both good HOR activity and stability. This work clarifies the critical role of B‐site cation doping in determining the Vo•• formation process, the surface activity, and structure stability of perovskite oxides. [ABSTRACT FROM AUTHOR]