A genuine dammarane glycoside, named ginsenoside Rg,, has been isolated by repeated column chromatography and preparative HPLC from the MeOH extract of Korean red ginseng (Panax ginseng C.A. Meyer). The chemical structure of ginsenoside Rg(5) was determined as 3-O-[beta-D-glucopyranosyl (1-->2)-beta-D-glucopyranosyl] dammar-20(22),24-diene-3 beta,12 beta-diol by spectral and chemical methods. The stereostructure of a double bond at C-20(22) of ginsenoside Rg, was characterized as (E) from the chemical shift of C-21 in the C-13-NMR and a NOESY experiment in the H-1-NMR.