<p>The effective recovery of valuable metals from waste lithium-ion batteries (LIBs) can promote synergistic growth in both economic and environmental domains. This study underscores the potential benefits of an environmentally sustainable approach that combines leaching and electrodeposition for the recovery of valuable metals from waste lithium-ion batteries. Specifically, it proposes a “citric acid + sodium thiosulfate” system for the effective extraction of valuable metals from waste LIBs along with the separation of Co and Li from the leaching solution via electrodeposition. High-purity LiCoO₂ powder was extracted following pretreatment. Optimal leaching conditions were established through one-way experiments, achieving leaching rates of 98% for both Co and Li. Kinetic studies indicate that leaching primarily involves a combination of surface chemical reactions and diffusive mass transfer. Density functional theory (DFT) investigations revealed that elemental cobalt in solution is predominantly stabilized in the form of cobalt citrate dimer. The separation of metals in the leach solution was achieved by removing cobalt metal via electrochemical analysis. The results demonstrate that the proposed method for the efficient extraction of valuable metals from waste LIBs, along with subsequent metal separation, offers a viable solution for recycling waste LIBs.</p>