Chemical energy storage is an attractive solution to secure a sustainable energy supply. It requires an electrocatalyst to be implemented efficiently. In order to rationally improve the electrocatalyst materials and thereby the reaction efficiency, one must reveal the nature of the electrocatalyst under reaction conditions, i.e., its active state. For a better understanding of earth-abundant metal oxides as electrocatalysts for the oxygen evolution reaction (OER), the combination of electrochemical (EC) methods and X-ray absorption spectroscopy (XAS) has been very insightful and still holds untapped potential. Herein, we concisely introduce the basics of EC and XAS and provide the necessary framework to discuss changes that electrocatalytic materials undergo, presenting manganese oxides as examples. Such changes may occur during preparation and storage, during immersion in an electrolyte, as well as during application of potentials without or with catalytic reactions. We conclude with a concise summary of how EC and XAS are currently combined to elucidate the active state as well as an outlook on future opportunities to understand the mechanisms of electrocatalysis using combined operando EC-XAS experiments.