Nine furostanol glycosides, namely caucasicosides E-M, were isolated from the MeOH extract of the leaves of Helleborus caucasicus, along with 11 known compounds including nine furostanol glycosides, a bufadienolide and an ecdysteroid. Their structures were established by the extensive use of 1D and 2D NMR experiments along with ESIMSn analyses. The steroidal composition of leaves of H. caucasicus shows as particular feature the occurrence of steroidal compounds belonging to the 53 series, unusual for Helleborus species, and in particular, caucasicosides F-H are based on a 5 beta-polyhydroxylated steroidal aglycon never reported before. (C) 2011 Elsevier Ltd. All rights reserved.