A detailed physico-chemical analysis of two foaming fungal fermentations was carried out to identify the key groups of compounds responsible for foam formation. Fermentations were carried out on a 20-L scale in a stirred aerated tank, over 7 days, using a commercial, defined medium. The organisms investigated were Penicillium herqueii, a hyphomycete, and an unidentified Ingoldian fungus. Samples of broth and, where possible, foam were analyzed to determine which groups of compounds were concentrated into generated foams. Surface tension, bulk viscosity, and antifoam A concentration were additionally determined in broth samples. To date the cause of foaming in fermentations has been attributed to the surfactant properties of extracellular proteins. This assumption was tested and found to be incomplete as many additional groups of biochemicals were found to be enriched into the foam. The results of the investigation revealed the presence of proteins, carbohydrates, ol-keto acids, and lipophilic biosurfactants, particularly extracellular pigments, enriched within stable foams.