Hemimorphite is important-supplementary resource for the commercial zinc production, but it easy loses into tailings due to extreme difficulty for its surface sulfidization. Adding active metal ions after sulfidization have been widely proposed for enhancing hemimorphite floatability, but its desired efficiency in flotation practice has not yet been completely achieved caused by the instability of sulfide layer. Whereas pre-adsorption of active metal ions to modify the hemimorphite surface has strong potential to make up for this shortcoming. Herein, the feasibility and appropriate environment of free Pb²⁺ for modifying the pure hemimorphite surface was evaluated. Subsequently, the performance of Pb²⁺ adsorption for enhancing sulfidization stability and floatability of hemimorphite were investigated. The X-ray photoelectron spectroscopy results indicated that the Pb²⁺ adsorption on hemimorphite surface was achieved through the Pb ions displacement for Zn ions, and it was bond to oxygen-containing groups on hemimorphite surface. Such adsorption was strengthened with the increasing of solution pH, owing to the abundant Pb hydroxyl species precipitated on mineral under alkaline conditions, in term of the results of visual MINTEQ modeling and time-of-flight secondary-ion mass spectrometry. In addition, the X-ray photoelectron spectroscopy results showed dominant Pb hydroxyl species further reacted with sulfur during subsequent sulfidization to generate much more S species than that of without Pb²⁺ pre-modification. Meanwhile, such sulfide layer composed by Pb²⁺ on the mineral surface presented much higher stability than Zn-S species, which was verified via adsorption and desorption tests. As a result, the sulfidization and flotation recovery of hemimorphite increased after Pb²⁺ pre-adsorption.