Summary: Deployment of electric vehicles with long driving ranges demands new electrochemistry beyond the current Li-ion batteries. Aprotic lithium–oxygen batteries have gained considerable attention and promise to provide energy density of approximately three to five times that of state-of-the-art Li-ion batteries, but they are plagued by sluggish reaction kinetics at cathodes and induced large-voltage hysteresis. A photo-mediated strategy has been attempted to reduce the discharge/charge overvoltage, but it is obstructed by the limited ultraviolet light absorption and the inevitably high carrier recombination on semiconductor photocathodes. Here, a plasmonic heterojunction of gold nanoparticle-decorated carbon nitride with nitrogen vacancies is used as a bifunctional catalyst to accelerate the oxygen cathode reactions of the lithium–oxygen battery under visible light. All study data are included in the article and/or [ SI Appendix ][1]. [1]: https://www.pnas.org/lookup/suppl/doi:10.1073/pnas.2024619118/-/DCSupplemental