Li-O₂ batteries with extremely high specific energy density have been regarded as a kind of promising successor to current Li-ion batteries. However, the high charge overpotential for the decomposition of Li₂O₂ discharge product reduces the energy efficiency and triggers a series of side reactions that cause the Li-O₂ batteries to have a limited lifetime. Herein, Co-doped C₃N₄ (Co-C₃N₄) photocatalysts were designed by an in situ thermal evaporation method to take advantage of the photo-assisted charging technology to conquer the shortcomings of Li-O₂ batteries encountered in the charge process. Different from the commonly used photocatalysts, the Co-C₃N₄ photocatalysts perform well no matter with and without illumination, owing to the Co doping induced conductivity and electrocatalytic ability enhancement. This makes the Co-C₃N₄ reduce the charge and discharge overpotentials and improve the cycling performance of Li-O₂ batteries (from 20 to 106 cycles) without illumination. While introducing illumination, the performance can be further improved: Charge voltage reduces to 3.3 V, and the energy efficiency increases to 84.84%, indicating that the Co-C₃N₄ could behave as a suitable photocathode for Li-O₂ batteries. Besides, the low charge voltage and the continuous illumination together weaken the corrosion of the Li anode, making the long-term high-efficiency operation of Li-O₂ batteries no longer just extravagant hope.