Three new triterpenoid saponins were isolated from the seeds of Aesculus chinensis, and characterized as 22-tigloylprotoaescigenin 3-O-[β-D-glucopyranosyl (1→2)] [β-D-glucopyranosyl (1→4)]-β-D-glucopyranosiduronic acid (escin IVg, 1), 22-angeloylprotoaescigenin 3-O-[β-D-glucopyranosyl (1→2)] [β-D-glucopyranosyl (1→4)]-β-D-glucopyranosiduronic acid (escin IVh, 2) and 16-angeloyl-21-acetylprotoaescigenin 3-O-[β-D-glucopyranosyl (1→2)] [β-D-glucopyranosyl (1→4)]-β-D-glucopyranosiduronic acid (escin VIb, 3), together with two known compounds, escin IIIa (4) and desacylescin I (5). Their structures were established on the basis of spectroscopic and chemical evidence.