The application of solar energy is crucial for alleviating the energy crisis and achieving sustainable development. In recent years, photo-assisted rechargeable batteries have attracted researchers because they can directly convert and store solar energy in the batteries. And it also can be used like a normal battery without light illumination. Photo-assisted lithium-based batteries have received more attention than other energy storage systems due to their higher energy density and relatively mature development. This Review focuses on the design of various photo-assisted lithium-based batteries including Li-ion, Li-S, Li-O 2 , Li-CO 2 and Li-I batteries, as well as the working mechanism of photoelectrodes in these battery systems. The basic understanding and challenge of photo-assisted lithium-based batteries are also discussed. At last, perspectives for the photoelectrode development are provided in the summary to advance photo-assisted energy storage systems.