From the fruits of Xeranthemum cylindraceum, Asteraceae–Cardueae, four known cyanogenic glycosides (sambunigrin, zierin, epilucumin, zierinxyloside) have been identified, two of these for the first time from this source. A fifth cyanogenic acylated trisaccharide, xeranthin, is a new compound; its structure has been elucidated by classical methods and by a combination of recent high field (14 Tesla, 600 MHz¹H) NMR correlation methods such as 2D¹Hdetected ¹³C NMR correlations.