A simple and efficient method was proposed to selectively separate and recover tellurium and bismuth in an acidic leaching solution of tellurium-bismuth ore by Na₂SO₃ and Fe powder. Then, the selective reduction mechanism was investigated by SEM-EDS, XRD, XPS, ICP-OES, etc. 99.83% Te in leaching solution can be reduced by Na₂SO₃ with an excess coefficient of 16 at 80 °C for 10 min, and the grade of crude tellurium can reach 93.78%. Besides, the stirring action can accelerate the reduction of Te because the dissolution of Na₂SO₃ is promoted. Subsequently, 99.39% Bi in the reduced solution can be displaced by Fe powder with an excess coefficient of 7.5 at 60 °C for 40 min, and the grade of crude bismuth can reach 92.35%. Finally, cyclic leaching of tellurium-bismuth ore was adopted to enrich Te(IV) and Bi(III) concentrations and decrease the Fe(III) concentration in leaching solution, which can efficiently decrease the consumption of Na₂SO₃.