This study systematically investigates the enhanced adsorption of sulfide species onto cerussite by surface modification with chloride through density functional theory calculations and X-ray photoelectron spectroscopy (XPS) measurements. Calculation results demonstrate obvious differences in the surface structures and electronic properties of cerussite after HS- adsorption in the absence and presence of chloride species. Surface modification with chloride promotes the stable adsorption of HS- onto the cerussite surface, and the hybridization of Pb 6p orbital at the surface layer and S 3p orbital from HS- is enhanced. Moreover, the reactivity of cerussite surfaces is enhanced by the occurrence of new DOS peaks of Pb 6p and S 3p near the Fermi level and by the transfer of additional electrons between the bonding atoms in the presence of chloride. Meanwhile, Mulliken population and XPS analysis results indicate that a slight oxidation is involved in the interaction between sulfide species and cerussite surfaces because of the presence of disulfide and polysulfide in the sulfidization products. In addition, a higher proportion of disulfide and polysulfide relative to the overall S is exhibited in the presence of chloride, facilitating the sulfidization flotation of cerussite. (C) 2017 Elsevier B.V. All rights reserved.