Twelve undescribed triterpenoid pentacyclic glycosides, medicagenic acid (3-O-β-D-glucuronopyranosyl-28-O-{[β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)]-[α-L-rhamnopyranosyl-(1 → 3)]-4-O-acetyl-β-D-fucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 3-O-β-D-glucuronopyranosyl-28-O-{[α-L-rhamnopyranosyl-(1 → 2)]-[β-D-apiofuranosyl-(1 → 3)]-4-O-acetyl-β-D-fucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 3-O-β-D-glucuronopyranosyl-28-O-{[α-L-rhamnopyranosyl-(1 → 2)]-3,4-O-diacetyl-β-D-fucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 28-O-{[6-O-acetyl-β-D-glucopyranosyl-(1 → 2)]-[2-O-acetyl-α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 28-O-{[6-O-acetyl-β-D-glucopyranosyl-(1 → 2)]-[3-O-acetyl-α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 28-O-{[6-O-acetyl-β-D-glucopyranosyl-(1 → 2)]-[4-O-acetyl-α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 28-O-{[6-O-acetyl-β-D-glucopyranosyl-(1 → 2)]-[β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid, 28-O-{[β-D-glucopyranosyl-(1 → 2)]-[β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-12-ene-23,28-dioic acid), zanhic acid (3-O-β-D-glucuronopyranosyl-28-O-{[β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)]-[α-L-rhamnopyranosyl-(1 → 3)]-4-O-acetyl-β-D-fucopyranosyl-(1→)}2β,3β,16α-trihydroxyolean-12-ene-23,28-dioic acid, 3-O-β-D-glucuronopyranosyl-28-O-{[β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)]-β-D-fucopyranosyl-(1→)}-2β,3β,16α-trihydroxyolean-12-ene-23,28-dioic acid), 29-hydroxy-medicagenic acid (3-O-β-D-glucuronopyranosyl-28-O-{[β-D-glucopyranosyl-(1 → 3)-α-L-rhamnopyranosyl-(1 → 2)]-[α-L-rhamnopyranosyl-(1 → 3)]-4-O-acetyl-β-D-fucopyranosyl-(1→)}-2β,3β,29β-trihydroxyolean-12-ene-23,28-dioic acid) and herniaric acid (28-O-{[6-O-acetyl-β-D-glucopyranosyl-(1 → 2)]-[α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranosyl-(1→)}-2β,3β-dihydroxyolean-18-ene-23,28-dioic acid) were isolated from the whole plant extract of Herniaria glabra L. (Caryophyllaceae), wild growing in the Ukraine. In addition, five known triterpenoid saponins; i.e. herniariasaponins 1, 4, 5, 6, and 7 were also isolated. Their structures were elucidated by HRESIMS, 1D and 2D NMR spectroscopy, as well as by comparison with the literature data. Twelve herniariasaponins, the purified crude extract, and the saponin fraction were evaluated in vitro for their xanthine oxidase, collagenase, elastase, and tyrosinase inhibitory activity. Moreover, herniariasaponins 4, 5, and 7 were screened for their cholinesterase inhibitory potential. As a result, no or low inhibition towards the mentioned enzymes was observed.