Electrocatalysts that start a reaction as molecules do not always end the reaction as molecules, and even when they do, they might not be molecules during catalysis. In this Perspective, we discuss knowledge learned from the study of Cu‐based molecularly structured electrocatalysts––including metal coordination complexes, metal‐organic frameworks, single‐atom catalysts, and polymeric materials––that restructure under electrochemical CO2 reduction reactions. Recent reports are summarized with an emphasis on the nature and significance of post‐mortem and in situ characterization for the proper identification of active sites.