In　the　flotation　beneficiation　of　copper　and　molybdenum　co-occurrence　ores,　the　efficient　depression　of　chalcopyrite　is　crucial　for　successful　copper-molybdenum　separation.　However,　the　consumption　of　conventional　depressant　NaHS　is　huge.　There　is　greater　susceptibility　of　chalcocite　and　other　secondary　copper　sulfide　minerals　to　electrochemical　reaction　in　comparison　to　chalcopyrite.　Given　the　irreversible　desorption　behavior　of　collector　molecules　on　chalcocite　upon　negative　potential　application,　electrochemically　regulated　flotation　can　be　effectively　utilized　to　diminish　the　utilization　of　conventional　depressants.　In　this　work,　electrochemistry　and　shell-separated　nanoparticle-enhanced　Raman　spectroscopy　(SHINERS)　were　used　to　explore　the　transformation　of　chalcopyrite　surface　to　chalcocite-like　species　under　the　combined　action　of　Cu2+　and　negative　potential.　The　results　show　that　the　similarity　of　cyclic　voltammetry　(CV)　between　the　modified　chalcopyrite　and　chalcocite,　increases　with　the　pretreatment　potential　becoming　increasingly　negative.　Electrochemical　impedance　spectroscopy　(EIS)　also　reflects　their　similar　adsorption　and　desorption　behavior　in　response　to　ammonium　dibutyl　dithiophosphate　(ADD),　a　typical　flotation　collector　molecule.　In　addition,　the　spectroelectrochemical　directly　reflects　the　irreversible　desorption　of　ADD　molecules　from　the　modified　chalcopyrite　surface　at　-　0.7　V.　The　research　results　lay　a　theoretical　foundation　for　the　efficient　Cu-Mo　separative　flotation　by　depressing　chalcopyrite　under　the　combination　of　Cu2+　and　negative　potential.