Solid oxide fuel cell technologies are essential for the storage of renewable energy and de-carbonisation. To push these technologies, a functional understanding of electrocatalytic materials under high-temperature conditions is imperative. Operando-based spectroscopic investigations, e.g., by near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) allow for unique insights into the chemical nature of active working electrodes, including the reactivity of different redox states and the adsorbate chemistry under dynamically changing electrochemical conditions. Thin-film model cells with spectroscopically accessible triple-phase boundary (TPB) regions for studies of interface states and local electrochemical processes deliver a fundamental understanding for the further development of renewable energy storage technologies.