The chemical composition of waste of small electrical and electronic equipment (s-WEEE), a rapidly growing waste stream, was determined for selected metals (Cu, Sb, Hg etc.) and non-metals (Cl, Br, P) and PCBs. During a 3-day experiment, all output products and the s-WEEE input mass flows in a WEEE recycling plant were measured. Only output products were sampled and analyzed. Material balances were established, applying substance flow analysis (SFA). Transfer coefficients for the selected substances were also determined. The results demonstrate the capability of SFA to determine the composition of the highly heterogeneous WEEE for most substances with rather low uncertainty (2σ ⩽±30%). The results confirm the growing importance of s-WEEE regarding secondary resource metals and potential toxic substances. Nowadays, the thirty times smaller s-WEEE turns over larger flows for many substances, compared to municipal solid waste. Transfer coefficient results serve to evaluate the separation efficiency of the recycling process and confirm – with the exception of PCB and Hg – the limitation of hand-sorting and mechanical processing to separate pollutants (Cd, Pb, etc.) out of reusable fractions. Regularly applied SFA would serve to assess the efficacy of legislative, organizational and technical measures on the WEEE.