The photoassisted lithium–oxygen (Li–O2) system has emerged as an important direction for future development by effectively reducing the large overpotential in Li–O2 batteries. However, the advancement is greatly hindered by the rapidly recombined photoexcited electrons and holes upon the discharging and charging processes. Herein, a breakthrough is made in overcoming these challenges by developing a new magnetic and optical field multi‐assisted Li–O2 battery with 3D porous NiO nanosheets on the Ni foam (NiO/FNi) as a photoelectrode. Under illumination, the photogenerated electrons and holes of the NiO/FNi photoelectrode play a key role in reducing the overpotential during discharging and charging, respectively. By introducing the external magnetic field, the Lorentz force acts oppositely on the photogenerated electrons and holes, thereby suppressing the recombination of charge carriers. The magnetic and optical field multi‐assisted Li–O2 battery achieves an ultralow charge potential of 2.73 V, a high energy efficiency of 96.7%, and good cycling stability. This external magnetic and optical field multi‐assisted technology paves a new way of developing high‐performance Li–O2 batteries and other energy storage systems. A renewable magnetic and optical field multi‐assisted Li–O2 battery is developed with porous NiO on the Ni foam as a photoelectrode. The battery achieves an ultralow charge potential of 2.73 V, a high energy efficiency of 96.7%, and good cycling stability. The effect mechanism of the improved battery performance with magnetic field and optical field is revealed.