Four polyhydroxylated and polyunsaturated furostanol glycosides (1–4), named caucasicosides A (1), B (2), C (3) and D (4), were isolated from the MeOH extract of the underground parts of Helleborus caucasicus, along with four spirostanol derivatives, a furostanol glycoside, a furospirostanol glycoside, 20-hydroxyecdysone and the bufadienolides hellebrigenin and deglucohellebrin. The structures of 1–4 were elucidated as furosta-5,20(22),25(27)-triene-1β,3β,11α,26-tetrol 26-O-β-d-glucopyranoside (1), 26-O-β-d-glucopyranosylfurosta-5,20(22),25(27)-triene-1β,3β,11α,26-tetrol 3-O-α-l-rhamnopyranosyl-(1→2)-β-d-glucopyranoside (2), 26-O-β-d-glucopyranosyl-22α-methoxyfurosta-5,25(27)-diene-1β,3β,11α,26-tetrol 3-O-α-l-rhamnopyranosyl-(1→2)-β-d-glucopyranoside (3), 26-O-β-d-glucopyranosylfurosta-5,20(22),25(27)-triene-1β,3β,26-triol 3-O-β-d-xylopyranosyl-(1→3)-α-l-rhamnopyranosyl-(1→2)-4-O-sulfo-α-l-arabinopyranoside (4). Structure elucidation was accomplished through the extensive use of 1D- and 2D NMR experiments including 1 H– 1 H (COSY, 1D-TOCSY) and 1 H– 13 C (HSQC, HMBC) spectroscopy along with ESI-MS and HR-ESI-MS. The aglycones of 1–4 have never been reported before.