The effects of arsenic with different valence states on the purification of copper electrolyte were studied and a novel technology of purification of copper electrolyte by copper arsenite was proposed. The results show that the purification performance of As(Ⅲ) compounds is better than that of As(Ⅴ) compounds. The purification technology by copper arsenite has the advantages of simple operation, high purification performance and low cost in comparison with other technologies and its appropriate purification conditions are that copper arsenite concentration is 18 g/L, reaction temperature is 65 ℃ and reaction time is 8 h. The removal rates of Sb and Bi are 53.22% and 58.67% respectively under these conditions. The purification principle show that a kind of yellow precipitate mainly composed of arsenic, antimony (Ⅴ), bismuth and oxygen forms in electrolyte after copper arsenite is added, and consequently antimony and bismuth are removed from electrolyte.