Experiments found that copper refining electrolyte can self-purify under certain conditions.The method of solution self-purification was applied in copper electrorefining commercial run and produced good results.By increasing copper electrolyte self-purification, the distribution ratios of the impurities As, Sb and Bi dissolved from copper anode and then deposited into the anode slimes were increased from 17.61%, 49.40% and 36.53% to 69.31%, 93.01% and 68.12% respectively.