The rechargeable lithium-air battery, with its high theoretical specific energy, holds significant potential for transforming energy storage. However, the fundamental chemistry and electrochemistry governing its operation, particularly at the cathode, have been poorly understood, hindering progress. This review discusses recent advances in understanding the mechanisms of oxygen reduction to Li₂O₂ during discharge and the reverse process during charge, as well as the various parasitic reactions involving the cathode and electrolyte. The stability of the cathode and electrolyte is also examined, along with design principles for improving lithium-air batteries. Key challenges include the stability of the electrolyte and cathode materials, the suppression of parasitic reactions, and the development of stable and conductive cathode materials. Recent studies have shown that altering the pathway of oxygen reduction can avoid the formation of LiO₂, which is reactive and can passivate the electrode, allowing for high rates and capacities. The use of soluble oxidation mediators is another promising approach to enhance charging efficiency. Despite these advancements, significant challenges remain, particularly in achieving stable and conductive cathode materials, and further research is needed to fully realize the potential of lithium-air batteries.The rechargeable lithium-air battery, with its high theoretical specific energy, holds significant potential for transforming energy storage. However, the fundamental chemistry and electrochemistry governing its operation, particularly at the cathode, have been poorly understood, hindering progress. This review discusses recent advances in understanding the mechanisms of oxygen reduction to Li₂O₂ during discharge and the reverse process during charge, as well as the various parasitic reactions involving the cathode and electrolyte. The stability of the cathode and electrolyte is also examined, along with design principles for improving lithium-air batteries. Key challenges include the stability of the electrolyte and cathode materials, the suppression of parasitic reactions, and the development of stable and conductive cathode materials. Recent studies have shown that altering the pathway of oxygen reduction can avoid the formation of LiO₂, which is reactive and can passivate the electrode, allowing for high rates and capacities. The use of soluble oxidation mediators is another promising approach to enhance charging efficiency. Despite these advancements, significant challenges remain, particularly in achieving stable and conductive cathode materials, and further research is needed to fully realize the potential of lithium-air batteries.