AbstractThe use of a sacrificial cathode additive that contains a large amount of lithium is one potential solution to compensate for the irreversible capacity loss associated with next‐generation anodes such as silicon. Antifluorite‐type Li₆CoO₄ has attracted attention as a potential cathode additive owing to its remarkably high theoretical lithium extraction capacity. However, the complex mechanism of lithium extraction as well as the oxygen loss from Li₆CoO₄ is not well understood. A generalizable computational thermodynamics and experimental framework is presented to understand the lithium‐extraction pathway of Li₆CoO₄. It is found that one lithium per formula unit can be topotactically extracted from Li₆CoO₄, followed by an irreversible and nontopotactic phase transformation to Li₂CoO₃ or LiCoO₂ depending on the temperature. The results show that peroxide species may form to charge‐compensate for Li extraction which is undesirable as this can lead to gas release during battery operation. It is suggested that charging Li₆CoO₄ at an elevated temperature that the electrolyte can withstand, redirects the reaction pathway and prevents the formation of intermediate peroxide species making it an effective and stable sacrificial cathode additive.