The selective electro-recovery of gold and silver values from cyanide leaching solutions containing copper was accomplished in a three-dimensional (3D) electrochemical reactor. This case let to contrast three different points of view when dealing with a composed metallic solution: First, the thermodynamic predictions; second, the microelectrolysis approach and finally, the macroelectrolysis experiments. Standard electrode potentials for the study solution would indicate a tendency for gold to deposit first. However, microelectrolysis studies of the three-metallic solution indicated that gold and silver are co-deposited onto a Vitreous carbon (VC) electrode without copper interference in a narrow potential range. Mass balances during the macroelectrolysis experiments (batch model assuming mass transfer control) indicated a preferential deposition of silver during the first ten minutes, even if gold deposition also occurred. On the other hand, values of Stanton (St) for different linear flow velocity corroborated that metals concentration gradients may establish a limit to make profitable the fluid velocity increase in an electrochemical flow cell. Electrolysis experiments were carried out under potentiostatic (at - 1400 mV versus SCE) and galvanostatic (at -3.9 Am-2) conditions in the FM-01 LC flow cell. (C) 2004 Elsevier Ltd. All rights reserved.