Antimony (Sb) powders and sulfur nanoparticles have been prepared by direct electroreduction of solid Sb2S3 in ChCl-EG DES at 353 K. Cyclic voltammogram of Sb2S3 on Pt-powder cavity microelectrode demonstrates that the electrochemical desulfurization of Sb2S3 to metallic Sb is a one-step process through three-electron transfer. Constant voltage electrolysis indicates that Sb2S3 can be completely transformed into metallic Sb and sulfur for 16 h, and the cathodic current efficiency is about 50.64%. Besides, ESI-MS analysis implies that four-coordinated complex anions [SbCl4](-) are formed and the electrodeposition of [SbCl4](-) -> Sb-0 also exists simultaneously except for the mainly direct desulfurization process. Dissolved Sb(III) ions can be reduced and deposited at Sb grains to form larger hemispherical particles in a more stable state, which looks like a snail shell to encapsulate these Sb grains. In addition, amorphous sulfur powders are densely agglomerated with each other to establish a network structure and the morphology is irregularly globular with diameters of 14-25 nm. The electro-desulfurization process of Sb2S3 powders has been analyzed and a schematic illustration is also proposed. This finding provides a possible way for green extraction of Sb from stibnite resources in DESs at near room temperature with short process and emission-free SO2. (C) 2019 The Electrochemical Society.