A novel process of tellurium recovering from high tellurium-bearing materials by alkaline sulfide leaching followed sodium sulfite precipitation is developed. The influences of Na 2 S concentration, leaching temperature, liquid to solid ratio and leaching time were studied during the leaching process while the effects of Na 2 SO 3 excess coefficient, reduction temperature and reduction time on tellurium precipitation from alkaline sulfide solutions were investigated. It was found that 91.24% of Te and 92.51% of Sb were extracted into leaching solution under the optimum conditions: Na 2 S concentration 100 g/L, 80 °C of leaching temperature, 10:1 mL/g of liquid to solid ratio and 60 min of leaching time. 98.85% of Te was precipitated selectively at 30 °C for 15 min with addition of 1.5-fold excess of Na 2 SO 3 while the antimony precipitation was closed to zero. XRD pattern and chemical analysis indicated that the precipitate was elemental tellurium with a purity of 99.11%. SEM image showed that the shapes of elemental tellurium were spindle with an average particle size of 1–2 μm. Antimony in Te-free solution was recovered as NaSb(OH) 6 by hydrogen peroxide oxidation. [ABSTRACT FROM AUTHOR]