Li‐O2 batteries with ultrahigh theoretical energy densities usually suffer from low practical discharge capacities and inferior cycling stability owing to the cathode passivation caused by insulating discharge products and by‐products. Here, a trifunctional ether‐based redox mediator, 2,5‐di‐tert‐butyl‐1,4‐dimethoxybenzene (DBDMB), is introduced into the electrolyte to capture reactive O2− and alleviate the rigorous oxidative environment of Li‐O2 batteries. Thanks to the strong solvation effect of DBDMB towards Li+ and O2−, it not only reduces the formation of by‐products (a high Li2O2 yield of 96.6 %), but also promotes the solution growth of large‐sized Li2O2 particles, avoiding the passivation of cathode as well as enabling a large discharge capacity. Moreover, DBDMB makes the oxidization of Li2O2 and the decomposition of main by‐products (Li2CO3 and LiOH) proceed in a highly effective manner, prolonging the stability of Li‐O2 batteries (243 cycles at 1000 mAh g−1 and 1000 mA g−1). A trifunctional ether‐based redox mediator, DBDMB, is introduced into the electrolyte to capture reactive discharge intermediates (O2−) with reduced formation of by‐products, regulate solution growth of Li2O2, and co‐oxidize Li2O2 and by‐products (Li2CO3 and LiOH). Li‐O2 batteries with large capacity and long cycling stability have been achieved.