The absolute stereostructues of cimicifugoside (1) and actein (2) from Cimicifuga simplex were established by X-ray crystal analysis of 26(S)-O-methylcimicifugenin A (1cS) prepared from 1, negative CD curves of 26-O-methyl-3-keto-cimicifugenins (1dS, 1dR), comparative analysis of 1H- and 13C-NMR spectra of 1, 2 and their derivatives, and preparation of 2 from 1 by hydrogenation : 20(R), 23(R), 24(R), 25(S), 26(R, S)-16β : 23; 23 : 26; 24 : 25-triepoxy-12β-acetoxy-3β, 26-dihydroxy-9, 19-cyclolanost-7-ene 3-O-β-D-xylopyranoside for 1 and 20(R), 23(R), 24(R), 25(S), 26(R, S)-16β : 23; 23 : 26; 24 : 25-triepoxy-12β-acetoxy-3β, 26-dihydroxy-9, 19-cyclolanostane 3-O-β-D-xylopyranoside for 2.