Aqueous chromium(VI) reduction and removal induced by glow discharge taking place at the gas–solution interface in an argon atmosphere was studied. The effect of initial pH and hydroxyl radical scavenger (ethanol) on the reduction efficiency was examined. High reduction efficiency was obtained when initial pH ≤ 2.0 or ≥ 8.0. In particular, addition of ethanol into the solution substantially increased the reduction efficiency and facilitated chromium removal from the solution in the form of sediment after discharge. The optimum pH values for Cr(VI) removal were within 6.0–7.0. Fourier transform-infrared (FTIR) spectroscopy and X-ray diffraction (XRD) analysis confirmed that the main constituent of the sediment is chromium hydroxide.