This work aims to contribute to the characterization of the electrodialysis (ED) of aqueous sulfuric acid-copper sulfate solutions. The presence of impurities such as As and Sb, typical of copper electrorefining electrolytes, is also studied. Results from kinetic studies carried out in ED cells with and without re-circulation are presented. The concentrations were: 3-9 gl(-1) copper, 50 gl(-1) sulfuric acid. 3 gl(-1) arsenic and 0.025 gl(-1) antimony; the temperatures, 22 and 44degreesC the transport rates, depending on experimental conditions, 0.2-0.6 mol h(-1) m(-2) of membrane for copper, 0.65-2.8 for sulfate, and 0.016-0.03 for arsenic. A speciation model has been developed and applied in order to interpret the experimental results and the performance of the studied cells has been evaluated. The main conclusion is that ED can be applied to the separation and concentration of chemical species in these systems.