A detailed analysis of the electrochemical behaviour of copper-loaded chloride solutions has been carried out by linear sweep and cyclic voltammetry. Similar copper concentration to pregnant solutions for electrowinning processing has been used and the influence of the relative content of metal- chloride ions on the copper deposition/dissolution reactions investigated. The study has shown that the redox-mechanism involves soluble cupric and cuprous species, and adsorbed cuprous chloride. Possible non-equilibrium processes occurring during the anodic dissolution of copper deposits are also discussed.