Simultaneous recovery of selenium and copper from waste sulfuric acid electrolyte is of great importance for industrial treatment of electrorefining effluents. In this study we developed a cost-effective electrochemical co-deposition method for recovering selenium and copper with microstructural refinement. In order to enhance the recovery ratio and to control the deposit quality, the synergistic effect of mass transfer intensification and thiourea addition towards electrochemical co-deposition was investigated systematically. We identified that the intensified mass transfer property has a beneficial effect from the kinetic considerations of electro-deposition while oscillation issues appear with the increase of the square root of the Reynolds number (Re-1/2). Furthermore, adding thiourea has an integrated effect between grain refining and kinetics frustration, which can prevent the formation of dendritic products and confine the metal ions under a highly turbulent flow. As a result, the most uniform and compact deposited products were obtained in the presence of appropriate stirring and additives with a satisfied recovery ratio.