The integrated design of solar energy conversion and storage systems has attracted increasing attention, and non-spontaneous redox reactions driven by dual photoelectrodes provide a potential solution to this issue. This study presents a solar rechargeable flow battery (SRFB) that combines dual photoelectrodes (BiVO4 or Mo–BiVO4 as photoanode, polyterthiophene (pTTh) as photocathode) with cost-effective redox pairs (Fe3+/Fe2+ and Br3−/Br−). The system charges under simulated solar illumination (100 mW∙cm−2, AM 1.5G) and releases stored energy controllably as electrical energy. Research indicates the Mo–BiVO4 photoanode and pTTh photocathode achieve an open-circuit voltage of 0.34 V and a short-circuit current density of 0.38 mA cm−2. Using a specially designed Fe3+/Fe2+-Br3−/Br− (Fe–Br) SRFB device made via 3D printing, a charging photocurrent of approximately 1.9 mA cm−2 is attained. In constant current discharge tests, an initial discharge voltage of 0.23 V is observed at 0.1 mA∙cm−2 within the 10 discharge cycles, demonstrating system stability and offering a viable solution for low-cost, large-scale solar energy storage and conversion.