Interfacial catalysis occurs ubiquitously in electrochemical systems, such as batteries, fuel cells, and photocatalytic devices. Frequently, in such a system, the electrode material evolves dynamically at different operating voltages, and this electrochemically driven transformation usually dictates the catalytic reactivity of the material and ultimately the electrochemical performance of the device. Despite the importance of the process, comprehension of the underlying structural and compositional evolutions of the electrode material with direct visualization and quantification is still a significant challenge. In this work, we demonstrate a protocol for studying the dynamic evolution of the electrode material under electrochemical processes by integrating microscopic and spectroscopic analyses, operando magnetometry techniques, and density functional theory calculations. The presented methodology provides a real-time picture of the chemical, physical, and electronic structures of the material and its link to the electrochemical performance. Using Co(OH) as a prototype battery electrode and by monitoring the Co metal center under different applied voltages, we show that before a well-known catalytic reaction proceeds, an interfacial storage process occurs at the metallic Co nanoparticles/LiOH interface due to injection of spin-polarized electrons. Subsequently, the metallic Co nanoparticles act as catalytic activation centers and promote LiOH decomposition by transferring these interfacially residing electrons. Most intriguingly, at the LiOH decomposition potential, electronic structure of the metallic Co nanoparticles involving spin-polarized electrons transfer has been shown to exhibit a dynamic variation. This work illustrates a viable approach to access key information inside interfacial catalytic processes and provides useful insights in controlling complex interfaces for wide-ranging electrochemical systems.