This paper reports an aqueous solar-charging redox battery (SCRB) with optimal redox couple combination, a single device that integrates a bromine-fenicyanide redox flow battery and solar cell through a linkage of KBr3/KBr positive electrolyte for simultaneous conversion and storage of solar energy. The battery can be directly charged upon 1 sun illumination (100.mW.cm(-2)), and discharge at an output voltage of 0.58 V delivering discharge capacity of 33.63 mAh/L and the solar energy conversion efficiency is 0.06%.