The charge compensation mechanisms that occur when Li+ substitutes a 2+ element in superionic conductor (MgCoNiCuZn)O high‐entropy oxide have been studied using a combination of thermogravimetric analysis and X‐ray photoemission spectroscopy. Depending on the concentration of Li+ in the compound, the charge compensation involves first partial oxidation of Co2+ into Co3+ for low fraction of Li+, and then a combination of both the oxidation of cobalt and the formation of oxygen vacancies for large fraction of Li+.