Bis-minerophilic　groups　can　improve　the　flotation　performance　of　the　collector　and　reduce　the　use　concentration.　In　this　study,　the　benzohydroxamic　acid　derivatives,　phthaloyl　hydroxamic　acid　(PHA),　isophthaloyl　hydroxamic　acid　(IHA),　and　terephthaloyl　hydroxamic　acid　(THA),　were　synthesized　and　first　introduced　as　the　collectors　in　the　flotation　separation　of　malachite.　Compared　with　the　traditional　collector,　benzohydroxamic　acid　(BHA),　their　collecting　abilities　to　malachite　were　followed　as　IHA　＞　BHA　＞　PHA　＞＞　THA.　For　the　artificial　mixed　mineral,　3.0　x　10(-4)　mol/L　IHA　without　Pb2+　ions　recovered　about　82　%　malachite,　23　%　calcite　and　17　%　quartz　at　pH　8.0.　Under　the　same　conditions,　their　recoveries　with　BHA　were　around　56　%,　17　%　and　15　%,　respectively.　The　contact　angle　and　adsorption　amount　results　exhibited　that　THA　could　adsorb　on　the　malachite　surface　but　could　not　enhance　its　surface　hydrophobicity.　The　ion　action　and　SEM　proved　that　PHA　would　corrode　the　malachite　surface,　resulting　in　unstable　adsorption.　XPS　and　DFT　revealed　that　the　suitable　molecular　structure　of　IHA　could　easily　chelate　with　the　Cu　atoms　to　form　two　five-membered　rings　due　to　its　stronger　electron-donating　ability　and　weaker　electron-accepting　ability.　This　study　provided　the　theoretical　support　for　the　design　and　application　of　novel　collectors　used　in　the　lead-free　flotation　enrichment　of　copper　oxide　resources.