The invention relates to a water-soluble organic couple redox flow battery which comprises an anode, electrolyte thereof, a diaphragm thereof, a cathode and electrolyte thereof, wherein one of two active substances of the anode/cathode is a water-soluble organic couple, and the other one is an inorganic couple or organic couple; and the electrolyte of the anode/cathode is stored in an external storage tank, flows through the battery in a circulating way through a pump and undergoes oxidation/reduction reaction on the anode/cathode divided by the diaphragm to carry out the charging/discharging process. Organic couple materials are not limited by mining deposits, the charge capacity depends on the volume of the storage tank, the size of the battery can be singly designed according to the power requirement, and electrode potential and a reaction electron amount can be designed and controlled by organic molecules. Therefore, the redox flow battery has the advantages of rich raw materials, convenient preparation, high power conversion efficiency, environmental protection, safe use and the like and is suitable for scale electricity storage.