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Electro‐ and photodriven catalysis are emerging as viable alternatives to traditional catalytic methods for producing key global consumer products across various applications. The emergence of this class of catalysis is attributable to increasing need for sustainable and ecofriendly pathways to value‐added chemical synthesis. The roadmap for the highly diverse and multifaceted field of catalysis continues to evolve, highlighting the growing need of understanding their physical and chemical reaction mechanism. Among the many available characterization techniques, in situ and operando investigations stand out for their ability to provide detailed insights into fundamental physicochemical processes under realistic working conditions. In this article, a select group of representative energy material is discussed, where the application of different in situ/operando techniques successfully generates improved understanding. The primary goal is to emphasize the significance of these techniques, particularly those, which have been commonly employed in studying materials relevant to energy and environmental applications.