ABSTRACTMetal organic frameworks (MOFs) have a promising perspective as oxygen evolution reaction (OER) electrocatalysts due to their high surface areas and tunable structures. However, one of the main challenges for their further application is inferior stability during alkaline OER. Herein, operando x‐ray absorption spectroscopy and operando x‐ray diffraction of NiCo‐MOF‐74 materials unveil their electrochemical transformations differentiating between electrolyte‐induced, beam‐induced, and electrochemically induced changes of the electronic state and local structure around the transition metal centers in addition to their overall crystal structure. An inferior electrolyte‐ and beam stability of Co‐MOF‐74 is revealed in comparison to a more stable performance of Ni‐MOF‐74 and Ni0.25Co0.75‐MOF‐74. Based on the operando measurement results, good experimental practices for future MOF OER electrocatalyst studies are presented.