As high-quality cassiterite resources dwindle, the significance of cassiterite associated with scheelite escalates. In this study, we synthesized a novel lead-group double ligand collector (Pb-BHA-SDBS) by introducing a new ligand, sodium dodecyl benzene sulfonate (SDBS), into the structure of lead complexes of benzohydroxamic acid (Pb-BHA). The flotation performance of Pb-BHA-SDBS was investigated by single-mineral flotation. The structural and chemical properties of Pb-BHA-SDBS were systematically investigated through FTIR, XPS, and quantum chemical calculations. The mechanism of enhancing cassiterite flotation with Pb-BHA-SDBS were investigated through adsorption energy analysis, XPS, AFM and contact angle analysis. The flotation recovery of cassiterite greatly increased from ≤30 % to ≥80 % when the Pb-BHA-SDBS is utilized as the collector. The FTIR and XPS results indicated that both SDBS and BHA form coordination bonds with lead ions, significantly strengthening the adsorption ability on the cassiterite surface. The adsorption of Pb-BHA-SDBS on the surface of cassiterite forms larger colloidal aggregates, further enhancing the roughness and hydrophobicity of the cassiterite surface, thereby strengthening the flotation of cassiterite.