Significance Lithium superoxide (LiO ₂ ) is an important intermediate in lithium–air batteries, a promising next-generation energy-storage platform. The conductivity, stability, and reactivity profiles of LiO ₂ are thought to play a crucial role in the cyclability of lithium–air batteries. We demonstrate that physical encapsulation of Li ₂ O ₂ with an appropriate redox-active molecule may be a viable strategy to access and stabilize LiO ₂ at room temperature while simultaneously protecting the solvent and electrolyte from deleterious reactivity derived from LiO ₂ . Encapsulation with a redox mediator does not impede interfacial electron and lithium-ion transport and provides researchers with a model system that recapitulates the charging of a lithium–air cell.