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In this particular paper, the emulsifying capacity of aqueous extracts from white beans is studied and the relationships between the composition and structure of the macromolecular components of the extracts and and their exerted emulsification ability are reported. The extracts are composed of three different populations: large polysaccharides (few MDa), proteins (tens of kDa) and smaller molecular entities (oligopeptides and oligosaccharides, polyphenols and salts, among other molecules). Proteins and smaller molecules adsorb onto oil-water interfaces, providing some emulsification capacity at pH 3 and sufficient emulsification at pH 7. Non-adsorbing polysaccharides, such as starch, cause depletion flocculation. In addition, Pickering phenomena are involved in the stabilization mechanism. SEC–MALLS/UV, confocal microscopy, zeta potential measurements and FT–IR data were used to obtain the results. Finally, there is a discussion of the particular characteristics of each population in emulsion stability, their relevance to culinary practice, and their potential as substitutes for artificial emulsifiers.