Abstract: The current study outlines the electrochemical recovery of tellurium from a metallurgical plant waste fraction, namely Doré slag. In the precious metals plant, tellurium is enriched to the TROF (Tilting, Rotating Oxy Fuel) furnace slag and is therefore considered to be a lost resource—although the slag itself still contains a recoverable amount of tellurium. To recover Te, the slag is first leached in aqua regia, to produce multimetal pregnant leach solution (PLS) with 421 ppm of Te and dominating dissolved elements Na, Ba, Bi, Cu, As, B, Fe and Pb (in the range of 1.4–6.4 g dm−3), as well as trace elements at the ppb to ppm scale. The exposure of slag to chloride-rich solution enables the formation of cuprous chloride complex and consequently, a decrease in the reduction potential of elemental copper. This allows improved selectivity in electrochemical recovery of Te. The results suggest that electrowinning (EW) is a preferred Te recovery method at concentrations above 300 ppm, whereas at lower concentrations EDRR is favoured. The purity of recovered tellurium is investigated with SEM–EDS (scanning electron microscope–energy dispersion spectroscopy). Based on the study, a new, combined two-stage electrochemical recovery process of tellurium from Doré slag PLS is proposed: EW followed by EDRR. Graphic abstract: [Figure not available: see fulltext.].