The　novel　amidoxime-based　collectors,　4-pyridylamidoxime　(PA),　3-ethyl-4-pyridylamidoxime　(EPA),　and　3methyl-5-tert-butyl-4-pyridylamidoxime　(MBPA),　were　introduced　in　the　lead-free　flotation　separation　of　wolframite　from　quartz　and　calcite.　Compared　with　PA,　EPA,　and　the　traditional　collector　benzohydroxamic　acid　(BHA),　MBPA　exhibited　a　better　separation　and　recovery　capacity　to　wolframite　ore.　4.0　x　10(-4)　mol/L　MBPA　recovered　more　than　80　%　wolframite,　similar　to　24　%　calcite,　and　similar　to　26　%　quartz　at　pH　8.0　without　Pb2+　ions.　Under　the　same　conditions,　BHA　only　floated　out　less　than　35　%　wolframite.　The　adsorption　amount　results　exhibited　a　stronger　adsorption　ability　of　MBPA　than　BHA　on　wolframite　surface.　Further,　the　results　of　zeta-potential,　FTIR,　XPS　and　density　functional　theory　(DFT)　calculation　revealed　that　MBPA　could　chemisorb　on　wolframite　surface　to　form　-N-Fe　and　-O-Fe　bonds.　MBPA　had　stronger　electron-donating　ability　and　weaker　electron-accepting　ability　than　BHA,　which　exhibited　higher　reaction　activity.　It　was　clear　that　MBPA　was　an　excellent　collector　in　the　lead-free　flotation　separation　of　wolframite　from　calcite　and　quartz.