Eighteen triterpene saponins (1-18) from Medicago arborea leaves have been isolated and their structures elucidated by spectroscopic, spectrometric (1D and 2D NMR, FAB-MS, ESI-MS/MS), and chemical methods. They have been identified as glycosides of medicagenic, zanhic, and 2beta-hydroxyoleanolic acids, soyasapogenol B, bayogenin, and 2beta,3beta-dihydroxyolean-12-en-23-al-28-oic acid. Twelve of them, identified as 3-O-beta-D-glucopyranosyl-28-O-[alpha-L-arabinopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside] zanhic acid (3), 3-O-beta-D-glucopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-[alpha-L-arabinopyranosyl-(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside] zanhic acid (4), 3-O-[alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl(1-->2)-beta-D-glucopyranosyl]-2beta-hydroxyoleanolic acid (5), 3-O-beta-D-glucuronopyranosyl-28-O-[alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]medicagenic acid (6), 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]bayogenin (9), 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]-2beta,3beta-dihydroxyolean-12-en-23-al-28-oic acid (10), 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-[beta-D-apiofuranosyl(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]zanhic acid (12), 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-[alpha-L-arabinopyranoside(1-->3)]-alpha-L-rhamnopyrano-syl(1-->2)-alpha-L-arabinopyranoside]zanhic acid (13), 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyrano-syl(1-->4)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]zanhic acid (14), 3-O-[alpha-L-arabinopyranosyl-(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranosyl]-28-O-[beta-D-xylopyranosyl(1-->4)-[beta-D-apiofurano-syl(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside]zanhic acid (16), 3-O-[beta-D-glucopyrano-syl(1-->2)-beta-D-glucopyranosyl]-28-O-[beta-D-xylopyranosyl(1-->4)-[alpha-L-arabinopyranosyl(1-->3)]-alpha-L-rhamno-pyranosyl (1-->2)-alpha-L-arabinopyranoside]zanhic acid (17), and 3-O-beta-D-glucuronopyranosyl-28-O-[beta-D-xylopyranosyl(1-->4)-[beta-D-apiofuranosyl(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyrano-side]medicagenic acid (18), are reported as new natural compounds. The presence of the aldehydic group on the sapogenin moiety of saponin 10 is discussed in the framework of a possible elucidation of the biosynthesis of these metabolites.