An analysis of the polar extracts from Allium ascalonicum L. led to the isolation of two new furostanol saponins (compound 1 and 2) and two known furostanol saponins (compound 3 and 4). On the basis of 1D and 2D NMR (including H-1, C-13 NMR, H-1-H-1 COSY, HSQC, TOCSY, HMBC, and NOESY), FAB-MS spectrometry, and chemical methods, their structures were elucidated as (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5 alpha-furost-2-one-3 beta, 5, 6 beta, 26-tetraol-3-O-alpha-L-rhamnopyranosyl-(1 -> 2)-beta-D-glucopyranoside (ascalonicoside C, 1), (25R)-26-O-beta-D-glucopyranosyl-22-methoxy-5 alpha-furost-2-one-3 beta, 5, 6 beta, 26-tetraol-3-O-alpha-L-rhamnopyranosyl-(1 -> 2)-beta-D-glucopyranoside (ascalonicoside D, 2), (25R)-26-O-,beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3 beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1 -> 4)-alpha-L-rhamnopyranosyl-(1 -> 4)-[alpha-L-rhamnopyranosyl-(1 -> 2)]-beta-D-glucopyranoside (dichotomin, 3), and (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3 beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1 -> 2)-[alpha-L-arabinofuranosyl-(1 -> 4)]-beta-D-glucopyranoside (parisaponin I, 4). Copyright (C) 2007 John Wiley & Sons, Ltd.