This paper deals with the separate electrochemical recovery of transition metals from battery black liquor. In a first approach, the authors investigated a model waste electrolyte mainly consisting of Cu, Co, Ni, and Mn in an acidic solvent, using citric acid as a complexing agent. An open porous Inconel® foam had been included as an electrode to benefit from the increased active surface area. Under the selected operation conditions, Cu was completely recovered, presenting almost 100% purity, while, in the case of Co, the purity was 96%, and a remanent concentration of about 1.2 g L−1 could still be determined.