Separating jamesonite and marmatite is difficult due to their similar response to traditional collectors. To improve the selectivity of the collector and simplify the reagent system, compound phosphate (MP) as a collector for the separation of jamesonite from marmatite was studied in this study. The flotation tests revealed that, compared with the most used butyl xanthate (BX), MP had the advantages of lower dosage and stronger selectivity under weak acid pulp. Under the optimum flotation conditions, a concentrate with the grade of 31.54% Pb, 6.93% Zn and the recovery of 89.87% Pb, 12.31% Zn could be obtained from mixed binary minerals flotation (mass ratio of 1:1). Adsorption, zeta potential, FT-IR and XPS analysis demonstrated that MP performed strong chemisorption on jamesonite surface while underwent weak physisorption on marmatite, this difference was responsible for the excellent selectivity of MP toward jamesonite flotation and weak collecting capacity to marmatite.