The present invention relates to a method of preparing a high-purity electrolyte solution for a vanadium redox flow battery using a catalytic reaction, and more specifically, to a method of preparing a high-purity electrolyte solution having a vanadium oxidation state of +3 to +5 from a mixture solution containing a vanadium precursor, a reducing agent, and an acidic solution, by using a catalyst. By using a catalyst and a reducing agent that does not leave impurities such as Zn2+, which are generated when preparing electrolyte solutions using an existing metal reducing agent, the high-purity electrolyte solution for a vanadium redox flow battery (VRFB) according to the present invention eliminates the need for an additional electrolysis process; does not form toxic substances during a reaction process, and thus is environmentally friendly; and is electrochemically desirable under milder process conditions than that of an existing process. In addition, the VRFB comprising the electrolyte solution prepared according to the present invention may be used to expand the utility of new renewable energy through price reduction of large-capacity energy storage devices.