The chemical structures of senegin-III (Ia), C₇₅, H₁₁₃O₃₅, [α]²⁰_D-6.6°(MeOH) and senegin-IV (Ib), C₈₁H₁₂₂O₃₉, [α]²⁰_D-20.2°(MeOH), which were isolated from Senegae Radix (root of Polygata senega LINN var. latifolia TORRY et GRAY), were established to be presenegenin-(3)-[β-D-glucopyranosyl]-(28)-{2-[β-D-galactopyranosyl (1_gal→4_xyl)-β-D-xylopyranosyl (1_xyl→4_rham)α-L-rhamnopyranosyl]-3-(α-L-rhamnopyranosyl)-4-(4'-methoxycinnamoyl)-β-D-fucopyranoside} and presenegenin-(3)-[β-D-glucopyranosy-1]-(28)-{2-[4-[β-D-galactopyranosyl-(1_gal→4_xyl)-β-D-xylopyranosyl]-3-[α-L-rhamnopyranosyl]-α-L-rhamnopyranosyl]-3-(α-L-rhamnopyranosyl)-4-(4'-methoxycinnamoyl)-β-D-fucopyranoside}, on the basis of physical data of both compounds and several of their derivatives and degradation products.