Protopanaxatriol saponins obtained with AB-8 macroporous resin mainly consisted of ginsenosides Rg(1) and Re. A novel mono-ester of ginsenoside-Rh(1) (ginsenoside-ORh(1)) was synthesized through further enzymatic hydrolysis and octanoyl chloride modifications. A 53% yield was obtained by a facile synthetic method. The structures were identified on the basis of 1D-NMR and 2D-NMR, as well as ESI-TOF-MS mass spectroscopic analyses. The isolated and synthetic compounds were applied in an anti-tumor bioassay, in which ginsenoside ORh(1) showed moderate effects on Murine H22 Hepatoma Cells.