Waste Electrical and Electronic Equipment (WEEE) is a key resource in the circular economy given its high concentration of valuable materials such as metals. The complexity of recycling this resource, however, is high due to different collection, separation and reprocessing steps. A combined Material Flow Analysis (MFA) and Life Cycle Assessment (LCA) can be used to optimise the environmental performance of this recycling chain. Whereas usually these methodologies are used post-factum, i.e. when data is available, this paper presents how MFA and LCA can be used to predict material flows and the potential environmental benefit of the recycling chain, guiding policy makers and industries towards effective decision making. Based on a case study in Flanders, Belgium, firstly, it is shown that currently only 32% of WEEE materials are recycled towards high-end applications whereas 68% is lost in low-end applications, landfill or incineration. Ferrous and non-ferrous metals such as aluminium and copper achieve the highest high-end material recoveries (54, 46 and 44% respectively), whereas precious metals and plastic achieve lower high-end material recoveries (21–38% and 20% respectively). Secondly, it is shown that the most promising factors to improve material recovery and environmental benefit are consumer behaviour and technological progress (mainly in separation technologies), both potentially doubling the current environmental benefit.