Abstract: Objective In order to reveal the structural properties of hemimorphite from the microscopic atomic level, first-principles calculations based on density functional theory were carried out. Method The band structure, density of states, Mulliken population, surface energy of different structures and differential charge density of hemimorphite were systematically analyzed. Result The high-energy electrons near the Fermi level in hemimorphite crystal are mainly contributed by the 2p orbit of O, with the best chemical reactivity, and easily become the mineral surface action site during flotation. There is substantial electron enrichment around O in the hemimorphite ore lattice and increased charge density. The electrons are missing from the outside of Zn and transferred to O, and the Zn-O bond exhibits the characteristics of an ionic bond. The population value of the Zn-O bond Mulliken is low, and the surface energy of the (1 1 0) surface broken along the Zn-O bond is minimum, and the polar ore (1 1 0) surface is the most likely cleavage surface exposed. Conclusion The research results systematically reveal the crystal and surface structure characteristics of hemimorphite, which can provide useful reference and guidance for the study of hemimorphite flotation behavior and the development of flotation reagents.