The use of rare earth elements (REEs) is increasing, mainly due to the growing demand for electric vehicles and new applications in green technology. This results in annual growth of the in-use REE stocks and the amount of End-of-Life (EoL) products containing REEs. REEs are considered critical elements by the EU, mainly because the rest of the world is dependent on China’s supply. Recycling of REEs can help alleviate the criticality of REEs, however, no REEs are currently functionally recycled. In this study, the time-dependent behavior of REEs in copper matte-slag system in primary copper smelting conditions was investigated experimentally at a laboratory scale. Lanthanum and neodymium were chosen to represent all REEs, as they are generally found in the highest concentrations in EoL products, and because REEs all have similar chemical behavior. The experiments were conducted as a function of time in air and argon atmospheres. SEM-EDS, EPMA and LA-ICP-MS methods were used for sample characterization. The results of this work indicate that the REEs strongly favor the slag and the deportment to the slag begins almost instantly when the system reaches high temperatures. With increasing contact times, the REEs distribute even more strongly into the slag phase, where they may be recovered and recycled, if their concentrations are sufficiently high and a suitable hydrometallurgical process can be found.