LAUSR

Photoassisted electrochemical reaction is regarded as an effective approach to reduce the overpotential of lithium–oxygen (Li–O2) batteries. However, the achievement of both broadband absorption and long term battery cycling stability are still a formidable challenge. Herein, an oxygen vacancy‐mediated fast kinetics for a photoassisted Li–O2 system is developed with a silver/bismuth molybdate (Ag/Bi2MoO6) hybrid cathode. The cathode can offer both double advantages for light absorption covering UV to visible region and excellent electrochemical activity for O2. Upon discharging, the photoexcited electrons from Ag nanoplate based on the localized surface plasmon resonance (LSPR) are injected into the oxygen vacancy in Bi2MoO6. The fast oxygen reaction kinetics generate the amorphous Li2O2, and the discharge plateau is improved to 3.05 V. Upon charging, the photoexcited holes are capable to decompose amorphous Li2O2 promptly, yielding a very low charge plateau of 3.25 V. A first cycle round‐trip efficiency is 93.8% and retention of 70% over 500 h, which is the longest cycle life ever reported in photoassisted Li–O2 batteries. This work offers a general and reliable strategy for boosting the electrochemical kinetics by tailoring the crystalline of Li2O2 with wide‐band light.