Clean hydrogen production via conventional water splitting requires sluggish anodic oxygen evolution, which can be replaced with more valuable electrosynthesis reactions. Here, we propose one novel strategy for coupling in-situ organic electrosynthesis with high-purity hydrogen production. A benzoquinone-derivative disodium 4,5-dihydroxy-1,3-benzenedisulfonate (Tiron)-o1 and a naphthoquinone-derivative 2,6,8-trismethylaminemethylene-3,5-dihydroxy-1,4-naphthoquinone (TANQ) were in-situ electrosynthesized and directly used in a flow battery without any further purification treatment. Constant, simultaneous production of TANQ and hydrogen was demonstrated for 61 hours, while stable charge-discharge capacities were retained for 1000 cycles. The work provided a new avenue for achieving in-situ ORAM synthesis and high-purity hydrogen.