Aprotic Li‐O2 batteries (LOB) with high theoretical energy density usually experience cathode clogging by insoluble Li2O2, along with high charge overpotential from its insulating nature. A dibenzo‐24‐crown‐8 aldehyde derivative (DB24C8A) is employed as an additive to enhance the binding strength with Li+, hence promoting the solubility of Li2O2. The generated [DB24C8A•Li+] avoids the parasitic reactions caused by reactive O2−. Thus, the LOB achieves a large discharge capacity of 6939 mAh g−1 at 200 mA g−1 and a high Li2O2 yield (≈93%). Moreover, DB24C8A facilitates the efficient decomposition of Li2O2 via Li+ coordination during the charge process, reducing the charge overpotential to 0.77 V and prolonging the lifetime of the LOB over 213 cycles at 1000 mAh g−1 and 500 mA g−1. This work provides a novel approach to boost the performance of LOB by incorporation of crown ether‐based compounds to regulate the Li2O2 growth and decomposition pathway.