This　paper　investigated　the　adsorption　mechanism　of　cupferron　on　the　malachite　(−2　0　1)　surface　and　the　implications　for　flotation　via　X-ray　photoelectron　spectroscopy　(XPS),　Fourier-transform　infrared　(FTIR)　measurements,　density　functional　theory　(DFT)　calculations,　and　microflotation　tests.　The　XPS　and　FTIR　analyses　confirmed　the　adsorption　of　cupferron　on　the　malachite　surface.　The　DFT　calculations　indicated　that　the　adsorption　was　mainly　due　to　the　reaction　between　O　atoms　in　cupferron　and　Cu　atoms　on　the　malachite　surface.　Six　different　adsorption　configurations　were　discussed,　and　the　Cu3-cupferron　anion-O1O2　model　was　the　most　stable.　The　five-membered-ring　cupferron-Cu　complex　was　produced　under　this　condition,　and　the　corresponding　adsorption　energy　is　−2.092　eV.　The　density　of　states　(DOS)　analysis　reveals　that　the　O　2p　orbital　from　cupferron　O　atoms　and　the　Cu　3d　orbital　from　malachite　Cu　atom　overlapped　at　−0.7　to　0.3　eV　and　−2.6　to　−0.8　eV　around　the　Fermi　level,　demonstrating　a　stable　chemical　adsorption.　The　population　analysis　showed　that　electron　transfer　occurred　between　the　Cu　and　O　atoms　during　the　adsorption　process.　The　micro-flotation　results　showed　that　cupferron　has　a　strong　collecting　performance　for　malachite.　This　research　provides　a　better　understanding　of　the　adsorption　mechanism　of　cupferron　on　malachite　surfaces　at　the　atomic　level.　It　is　of　great　significance　for　its　application　in　flotation.　©　2021　Elsevier　Ltd