A new saponin, malonylginsenoside Ra3, was isolated from the fresh root of Panax ginseng, along with four known ginsenosides. The new compound was identified as (20S)-protopanaxadiol-3-O-(6-O-malonyl-beta-D-glucopyranosyl(1-->2)-beta-D-glucopyranoside-20-O-beta-D-xylopyranosyl(1-->3)-beta-D-glucopyranosyl(1-->6)-beta-D-glucopyranoside on the basis of extensive 1D and 2D NMR as well as HRESI-MS spectroscopic data analysis.