Tetrahedral, pyramidal, and octahedral metal-oxygen coordinated ligands are fundamental components in all metal-oxide structures. Understanding the impacts of their spatiotemporal behaviors during electrochemical oxidation is crucial for diverse applications, yet remains unsolved due to challenges in designing model oxides and conducting operando characterizations. Herein, combining a suite of advanced operando characterizations and systematic computations, a link between oxygen-evolving performance and operational structural properties is established on model oxides. Compared with tetrahedral and octahedral structures, pyramidal structure is more susceptible to OH