The effectiveness of electrodialysis (ED) for (a) the separation of Cu and Fe and (b) water recovery from solutions analogous to those found in copper electrowinning operations, has been studied. A five-compartment ED cell with recirculation of the electrolytes and a synthetic solution, similar to a copper electrowinning electrolyte, were used. The experimental variables were: applied current density, recirculation flow rate and time of operation. Ion removal rates from the working solution increased with cell current density and solution flowrate. ED proved very effective in the removal of Cu and Fe from the working solution, which means that water can be recovered from these electrolytes.