Extraction of lead and antimony from their sulfides without SO 2 emission is of great significance to tackle the air pollution caused by the conventional metallurgical routes. In the paper, solid PbS and Sb 2 S 3 are respectively electrochemically reduced to Pb and Sb in a 50 wt% NaOH solution. Thermodynamic analysis is conducted to illustrate the feasibility of extracting metals from their sulfides in the alkaline solution. Moreover, a home-made graphite cavity working electrode was employed to study the electrochemical reduction behaviors of PbS and Sb 2 S 3 , and their reduction processes were in situ recorded by a camera in a transparent cell. The results show that the strong alkaline solution is able to electrochemically convert PbS and Sb 2 S 3 into Pb and Sb with a current efficiency higher than 90%.