The structure of a new steroidal alkaloid from Solanum neocardenasii, solanocardinol, has been characterized by mass spectrometry, 2D-NMR and chemical methods. In contrast to the closely related spirofuranopiperidine the configuration of this compound at C-16 is β. The relevance of solanocardinol to the chemotaxonomy of Solanum species is discussed. © 1991.