The marine sponge Spheciospongia vesparia produces ves-parioside (1a), a diglycosylated glycosphingolipid which is the first example of a natural diglycosylceramide with a pentose sugar residue. The structure of vesparioside was mostly determined by extensive spectroscopic analysis but determination of the nature of the alkyl chains and elucidation of the absolute stereochemistry of the sugars and of the ceramide required chemical degradation. In this respect, an improved and simplified procedure for the microscale chemical degradation of glycosphingolipids was employed here for the first time. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).