Lithium-ion batteries (LIBs) are a tremendous achievement in the current energy storage landscape. However, there is an increasing demand for their implementation due to a variety of applications, such as mobile devices and a growing market of electric vehicles. Hence, the recycling of end-of-life batteries is one of the ways to satisfy the need for manufacturing new ones; however, this is challenging due to the lack of sustainable and efficient methods on a large scale. Electrochemical methods are widely used in the production of metals and alloys, therefore constituting a promising way for the recovery of critical metals present in cathode materials in LIBs. In this work, cathode materials have been collected from used LIBs from different sources and leached altogether with sulphuric acid and hydrogen peroxide. The resulting solution was treated electrochemically by applying a constant potential of-0.5 V for 20 h, which promoted the selective separation of copper and manganese at the cathode and anode sides, respectively. Complete and selective recoveries of Cu and Mn were proved by ICP-OES methods, while the purity of the obtained products was assessed by XRD, oS and SEM-EDS analysis. This investigation presents a great potential for the implementation of an electrochemical treatment to recover valuable metals in pure and ready to reuse form from spent LIBs, which can be easily scaled-up as an alternative to current non-green recovery processes.