Investigation of the benzopyranones from the roots of PELARGONIUM SIDOIDES led to the identification of 15 benzopyranones, among them the novel compounds 12 and 14. Furthermore, benzopyranones 4 and 15 were detected in PELARGONIUM SIDOIDES for the first time. Structure determinations were performed by one- and two-dimensional NMR spectroscopy. An HPLC system for the discrimination of these benzopyranones has been developed.