A radical compound, it can be produced at low temperature in matrix isolation experiments, or in certain nonpolar, non-protic solvents.

Lithium superoxide is also a transient species during the reduction of oxygen in a lithium–air galvanic cell, and serves as a main constraint on possible solvents for such a battery.

[7] Lithium superoxide also appears at the cathode of a lithium-air galvanic cell during discharge, as in the following reaction:[8] This product typically then reacts and proceed to form lithium peroxide, Li2O2 The mechanism for this last reaction has not been confirmed and developing a complete theory of the oxygen reduction process remains a theoretical challenge as of 2022[update].

[10] A significant challenge when investigating these batteries is finding an ideal solvent in which to perform these reactions; current candidates are ether- and amide-based, but these compounds readily react with the superoxide and decompose.

[9] Nevertheless, lithium-air cells remain the focus of intense research, because of their large energy density—comparable to the internal combustion engine.