Abstract: The lead-benzohydroxamic acid complex (Pb−BHA), a typical novel metal-organic framework (MOF) collector, exhibits high selectivity for the flotation of oxide minerals such as scheelite, cassiterite, and ilmenite. Owing to its poor foaming performance, it is typically used synergistically with frothers such as terpineol. However, their foaming properties and adsorption behavior at the air-water interface remain insufficiently investigated, which limits the in-depth understanding of their flotation mechanism and practical application. This study investigated the effects of Pb−BHA colloidal collector and its combination with terpineol on flotation foam performance and the underlying adsorption mechanisms at the air-water interface via froth stability tests, bubble size measurements, micro-flotation tests, Hirshfeld surface analysis, Sum Frequency Generation (SFG), surface tension measurements, and Molecular Dynamics (MD) simulations. The results demonstrated that Pb−BHA exhibited poor foaming ability, with its intermolecular N−H···O hydrogen bonds facilitating interactions with water molecules, leading to its distribution within the liquid phase near the air-water interface and exert minimal influence on surface tension. However, when Pb−BHA coexisted with terpineol, hydrogen bonding between the two components led to the formation of aggregates at the interface, with Pb−BHA located in the liquid phase and terpineol in the gas phase. These aggregates, with larger spatial volumes, reduced surface tension and bubble size more effectively than terpineol alone, significantly enhancing foam stability and flotation recovery. Notably, this synergistic interaction substantially improved scheelite flotation, increasing recovery from 40.21% to 91.74% and resulting in more stable froth. This study provides both theoretical and practical foundations for the molecular design of high-efficiency MOF collectors and the regulation of froth stability in flotation processes.