Consumer concerns about synthetically derived food additives have increased current research efforts to find naturally occurring alternatives. This review focuses on a group of natural surfactants, the Quillaja saponins, that can be extracted from the Quillaja saponaria Molina tree. Quillaja saponins are triterpenoid saponins comprising a hydrophobic quillaic acid backbone and hydrophilic sugar moieties. Commercially available Quillaja saponin products and their composition and properties are described, and the technofunctionality of Quillaja saponins in a variety of food, cosmetic, and pharmaceutical product applications is discussed. These applications make use of the biological and interfacial activities of Quillaja saponins and their ability to form and stabilize colloidal structures such as emulsions, foams, crystallized lipid particles, heteroaggregates, and micelles. Further emphasis is given to the complexation and functional properties of Quillaja saponins with other cosurfactants to create mixed surfactant systems, an approach that has the potential to facilitate new interfacial structures and novel functionalities.