Hassan Shabbir, Annam Butt, Chun‐Chen Yang, Rajan Jose
ABSTRACT Aprotic lithium‐oxygen batteries (LOBs) offer a theoretical energy density comparable to liquid fuels (∼3500 Wh·kg−1), but their practical deployment is limited by sluggish oxygen electrochemistry, insulating discharge products, parasitic reactions, and lithium‐metal instability. This review critically examines recent advances in addressing these challenges through a synergistic approach that integrates bifunctional catalysts, redox mediators, electrolyte engineering, and interface modification. Drawing from over 350 recent publications, with a diverse choice of cathode catalysts, electrolytes, and redox mediators, we highlight how catalyst‐redox mediator coupling, electrolyte stabilization, and separator design can collectively enhance oxygen reaction kinetics, reduce charge overpotentials, and suppress degradation pathways. Particular attention is given to the mechanistic role of LiO 2 disproportionation, singlet oxygen formation, and redox mediator shuttle effects in dictating reversibility and cycle life. These findings underscore that isolated component optimization is insufficient; instead, a system‐level design strategy that couples cathode, electrolyte, anode, and separator innovations is essential. By mapping recent progress and identifying persisting bottlenecks, this review provides a roadmap for advancing LOBs from laboratory prototypes toward efficient, stable, and commercially viable next‐generation energy storage systems.