Electrochemical carbon dioxide (CO2) reduction (ECR) is a promising technology to produce valuable fuels and feedstocks from CO2. Despite large efforts to develop ECR catalysts, the investigation of the catalytic performance and electrochemical behavior of complex metal oxides, especially perovskite oxides, is rarely reported. Here, the inorganic perovskite oxide Ag-doped (La0.8Sr0.2)0.95Ag0.05MnO3–δ (LSA0.05M) is reported as an efficient electrocatalyst for ECR to CO for the first time, which exhibits a Faradaic efficiency (FE) of 84.3%, a remarkable mass activity of 75 A g−1 (normalized to the mass of Ag), and stability of 130 h at a moderate overpotential of 0.79 V. The LSA0.05M catalyst experiences structure reconstruction during ECR, creating the in operando-formed interface between the perovskite and the evolved Ag phase. The evolved Ag is uniformly distributed with a small particle size on the perovskite surface. Theoretical calculations indicate the reconstruction of LSA0.05M during ECR and reveal that the perovskite–Ag interface provides adsorption sites for CO2 and accelerates the desorption of the *CO intermediate to enhance ECR. This study presents a novel high-performance perovskite catalyst for ECR and may inspire the future design of electrocatalysts via the in operando formation of metal–metal oxide interfaces.@en

Oxygen-ion conducting perovskite oxides are important functional materials for solid oxide fuel cells and oxygen-permeable membranes operating at high temperatures (>500 °C). Co-doped perovskites have recently shown their potential to boost oxygen-related kinetics, but challenges remain in understanding the underlying mechanisms. This study unveils the local cation arrangement as a new key factor controlling oxygen kinetics in perovskite oxides. By single- and co-doping Nb5+ and Ta5+ into SrCoO3-δ, dominant factors affecting oxygen kinetics, such as lattice geometry, cobalt states, and oxygen vacancies, which are confirmed by neutron and synchrotron X-ray diffraction as well as high-temperature X-ray absorption spectroscopy, are controlled. The combined experimental and theoretical study unveils that co-doping likely leads to higher cation dispersion at the B-site compared to single-doping. Consequently, a high-entropy configuration enhances oxygen ion migration in the lattice, translating to improved oxygen reduction activity.@en