Two triterpenoid saponins (compound Ⅰ and Ⅱ) have been isolated from Gymnocladus chinensis Baill., and compound Ⅰ was determined as a new compound. The structure of compound Ⅰ was assigned as 2β,23-dihydroxy-acacic acid-3-O-α-L-arabinopyranosyl-21-O-{(6S)-2-E-2,6-dimethyl-6-O-[4-O-(6S)-2-E- 2,6 -dimethyl-6-O-β-D-glucopyranosyl-α-L-arabinopyranosyl-2,7-octadienoyl} -28-O-β-D-xylopyranosyl( 1 →3 )-β-D-xylopymnosyl ( 1→4)- α-L-rhamnopyranosyl(1→2)-[α-L-rhamnopyranosyl-(1→6)]-β-D-glucopyranoside by extensive MS and NMR studies.