A novel benzofuran derivative (R)-(+)-Ligulaodonin A (1) and a new olean-12-ene triterpene (5), as well as 10 known compounds were isolated from the whole plant of Ligularia odontomanes HAND.-MAZZ. The structures of the new compounds were determined by spectroscopic evidence, including IR, UV, EI-MS, positive HR-ESI-MS, 1D-NMR and 2D-NMR. The absolute configuration of 1 was elucidated on the basis of circular dichroism (CD) data.