Integrating both photoelectric-conversion and energy-storage functions into one device allows for the more efficient solar energy usage. Here we demonstrate the concept of an aqueous lithium iodine (Li-I) solar flow battery (SFB) by incorporation of a built-in dye-sensitized TiO2 photoelectrode in a Li-I redox flow battery via linkage of an I-3(-)/I- based catholyte, for the simultaneous conversion and storage of solar energy. During the photoassisted charging process, I- ions are photoelectrochemically oxidized to I-3(-), harvesting solar energy and storing it as chemical energy. The Li-I SFB can be charged at a voltage of 2.90 V under 1 sun AM 1.5 illumination, which is lower than its discharging voltage of 3.30 V. The charging voltage reduction translates to energy savings of close to 20% compared to conventional Li-I batteries. This concept also serves as a guiding design that can be extended to other metal-redox flow battery systems.