All-vanadium redox flow battery (VRFB) is a large-scale electrochemical energy storage technology with numerous potential applications because of its inherent safety and long service life. In previous years, a novel mixed-acid electrolyte system, vanadium electrolytes with mixture of sulfuric acid and hydrochloric acid, has been developed by the Pacific Northwest National Laboratory (PNNL) to increase vanadium solubility, which can effectively raise the electrolyte energy density from 25 Wh/L to 40 Wh/L. To further improve mixed-acid VRFBs, in present work, high purity mixed-acid electrolytes were prepared using a novel direct dissolution - electrochemical reduction process from high purity vanadium oxytrichloride (VOCl3). And the purity and electrochemical properties were investigated, comparing with common mixed-acid electrolytes and regular sulfate electrolytes prepared from metallurgical grade vanadium pentoxide. It was found that the novel process demonstrated a great potential for the low cost and high efficiency production of high purity electrolytes with excellent electrochemical properties for mixed-acid VRFBs. Comparing the traditional high purity electrolytes preparation process, the present novel method will dramatically cut the cost by more than 90 percent, which will considerably facilitate the commercial application of high performance and high density VRFBs.