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The hydrogen evolution reaction in the negative half-cell of a vanadium redox battery is studied at a graphite electrode. Hydrogen evolution behavior is included by potentiostatic method. It is found that volume of hydrogen evolution goes up linearly at the first stage and then increases slowly at different polarization potential, concentration of sulfuric acid and V3+. The reason is adsorption hydrogen on graphite surface, with a trend toward an increase in electrical resistance and a decrease in the active surface area. The surface morphology and structural properties of graphite are investigated by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of graphite is observed using cyclic voltammetry and impedance spectroscopy (EIS). It is shown that hydrogen evolution reaction changes surface morphology and introduces some defect sites on the surface of graphite. The electrochemical activity of graphite towards V3+/V2+ couple becomes less easily after hydrogen evolution treatment.