The actaplanins are a family of glycopeptide antibiotics having a common aglycon but differing in their content and/or distribution of attached sugar units. Sites of sugar attachment in the actaplanins have been determined by NMR methods, including the observations of negative nuclear Overhauser effects. These results, when combined with information from the analysis of sugar content and from the observation of common acidic degradation pathways, have led to an explanation of the structures of the various actaplanin glycopeptides. All of the actaplanins contain ristosamine attached to the aglycon via a benzylic hydroxyl group, and they all contain either one or two mannose moieties, attached as monosaccharides at phenolic sites. An additional phenolic site in each actaplanin is occupied by either glucose, mannosylglucose, or rhamnosylglucose.