The realization of practical aprotic Li−O₂ batteries is hindered by superoxide‐related parasitic reactions and high overpotentials. Herein, a heme‐based nanozyme containing iron‐porphyrin derivative ligands is used as a novel electrolyte additive to scavenge superoxide radicals in the Li−O₂ system. Specially, this type of nanozyme can act as a bifunctional catalyst for both discharge and charge by coordinating with superoxide intermediates, functioning as a molecular shuttle of superoxide species and electrons between cathodes and products. As a consequence, the Li−O₂ batteries exhibit boosted discharge capacity, reduced charge polarization and superior cycling stability in the presence of the nanozyme additive. This first attempt to using nanozyme in Li−O₂ batteries should pave a new way for the sustainable cross‐link between biomimetic enzymes and advanced energy storage.