Interfacial interactions involving Van der Waals force, hydrophobic attractive force and hydration exclusive force were investigated in this paper. The interfacial interactive free energy of a series of interfaces occurring between minerals, water, collectors and bubble was calculated. The results show that a Van der Waals attractive force and a hydrophobic attractive force exist between each mineral and water interface. The hydrophobic attractive force between molybdenite and water is markedly weaker than the hydrophobic attractive force between gangue and water. The hydrophobic attractive force between collector molecules and water is the main driving force that causes the collectors to become dispersed in the pulp. The strong hydrophobic attractive force between molybdenite and the bubble interface is the basic reason for the natural floatability of molybdenite. The Van der Waals force between molybdenite and the collectors is attractive in water solution, but it is not the cause of the main force between them. The main force that results in the collection effect is a hydrophobic attractive force caused by the Lewis acid-base interaction at the molybdenite surface. A floatation experiment shows that the adsorption intensity of the collector on the molybdenite surface is not the crucial factor for molybdenite floatation. Rather, the dispersing capability of the collector in the water phase and its selectivity for the various minerals in the floatation system are more important. Interfacial interactions involving Van der Waals force, hydrophobic attractive force and hydration exclusive force were investigated in this paper. The interfacial interactive free energy of a series of interfaces occurring between minerals, water, collectors and bubble was calculated. The results show that a Van der Waals attractive force and a hydrophobic attractive force exist between each mineral and water interface. The hydrophobic attractive force between molybdenite and water is markedly weaker than the hydrophobic attractive force between gangue and water. The hydrophobic attractive force between collector molecules and water is the main driving force that causes the collectors to become dispersed in the pulp. The strong hydrophobic attractive force between molybdenite and the bubble interface is the basic reason for the natural floatability of molybdenite. The Van der Waals force between molybdenite and the collectors is attractive in water solution, but it is not the cause of the main force that results in the collection effect is a hydrophobic attractive force caused by the Lewis acid-base interaction at the molybdenite surface. A floatation experiment shows that the adsorption intensity of the collector on the molybdenite surface is not the crucial factor for molybdenite floatation. Rather, the dispersing capability of the collector in the water phase and its selectivity for the various minerals in the floatation system are more important.