The sulfidization performance and mechanism of hemimorphite surface in a sodium sulfide (Na₂S) system were revealed, and surface sulfidization products were identified through various analytical methods. The results showed that Na₂S concentration had a significant effect on the sulfidization of the hemimorphite surface. An increase in Na₂S concentration could promote the interaction between S species in the pulp and mineral surfaces, thereby increasing the content of sulfidization products and hydrophobicity of hemimorphite surface. XPS and ToF-SIMS analyses showed that the sulfidization product was not the sole monosulfide on hemimorphite surfaces and it was composed of monosulfide (S^2-) and polysulfide (S_n^2-). The content of polysulfide on mineral surface increased with an increase in the Na₂S concentration, which improves the activity of sulfidization products on hemimorphite surface.