Cyclic voltammetry was used to characterize the behaviour of silver-bearing copper anodes during electrorefining. Reproducible electrochemical characteristics were obtained for copper anodes of different shapes, sizes and configurations (vertical against horizontal) containing up to 1 wt % silver. Passivation time measurements indicated a strong correlation between the electrochemical spectra characteristics and the ease of anode passivation. A cubic-shaped anode without acrylic mounting medium was developed that avoided the impact of anode size End shape on the electrochemical characteristics and passivation of silver-bearing copper anodes. A fully computerized data acquisition system previously developed to generate electrochemical spectra for pure copper anodes under simulated electrorefining conditions has been extended to the examination of silver-bearing copper anodes.