Arsenic is the only beneficial impurity for copper electrorefining through inhibiting anode passivation and the formation of floating slimes. The behaviour of copper anodes with different content of arsenic were studied at high current density (>280 A/m ²). It showed that low arsenic anodes (As < 300 ppm) easily generated anode passivation, floating slimes and cathode nodules during the electrorefining proccess. The floating slimes, electrolyte, cathode and anode were observed and analyzed. As result, low arsenic anodes were more likely to be passivated due to their microstructure defects and irregular microstructure. Increasing electrolyte temperature and addition of glycerol were propitious to reduce low arsenic anodes’ passivation. The floating slimes occured when the concentration of As(III) in electrolyte decreased to 1 g/L, and they would be precipitated by polyacrylamide. All measures greatly improved the cathode quality at current density of 300 A/m ².