In this work, the growth of copper sulfide crystal onto azurite surfaces during sulfurization and its response to flotation are investigated. Filed emission scanning electron microscopy-energy dispersive X-ray spectroscopy (FESEM) and X-ray diffraction (XRD) studies confirmed that the sulfurization of azurite is not limited to the mineral surface, but rather penetrates into the bulk to form covellite crystal (syn-CuS), creating favorable conditions for the stable adsorption of xanthate and greatly promoting the azurite flotation. Additionally, as demonstrated by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS) analyses, a redox reaction occurred during this process, and Cu(II) onto the mineral surface was reduced to Cu(I). Correspondingly, reduced S2- was oxidized to (S-2)(2-), (S-n)(2-), and even to deeper oxidation state S-0, (SxOy)(n-) and SO42-. Excess sodium sulfide strengthens copper sulfide to form onto the azurite surface, and provides enough raw material for crystal copper sulfide to grow, resulting in the formation of "flake-like" covellite with a better crystallinity. However, the floatability of azurite decreased dramatically under this condition, because the generated massive colloidal copper sulfide in flotation pulp deteriorates the flotation environment, resulting in a decreased effective adsorption of collector onto azurite surfaces. (C) 2021 Published by Elsevier B.V. on behalf of China University of Mining & Technology.