The similar floatabilities of calcium minerals and the huge difference between scheelite and wolframite have resulted in difficulties during their separation by flotation in Shizhuyuan Mine. In this study, novel collectors, lead complexes of benzohydroxamic acid(Pb–BHA),were introduced to modify the surface properties of scheelite and wolframite, thereby effectively and selectively improving floatability. The Pb–BHA complexes are found to be selective for the separation of scheelite and calcium minerals with little use of depressants and enable the synchronous flotation of scheelite and wolframite.Hence, a novel flotation process was developed for the recovery of tungsten minerals. The process is simplified greatly, and the recovery is improved by almost 10%.Removing or decreasing the amount of water glass contributes to the improvement of tungsten and fluorite recovery and the circulation of water and reagents, which benefits the environment. The similar floatabilities of calcium minerals and the huge difference between scheelite and wolframite have resulted in difficult during their separation by flotation in Shizhuyuan Mine. In this study, novel collectors, lead complexes of benzohydroxamic acid (Pb-BHA), were introduced to modify the surface properties of scheelite and wolframite, effectively and successively improving floatability. The Pb-BHA complexes are found to be selective for the separation of scheelite and calcium minerals with little use of depressants and enable the synchronous flotation of scheelite and wolframite .ence, a The process is simplified greatly, and the recovery is improved by almost 10%. Removing or decreasing the amount of water glass contributes to the improvement of tungsten and fluorite recovery and the circulation of water and reagents, which benefits the environment.