The methanol-eluted fraction of the methanolic extract from the tubers of Gymnadenia conopsea was found to show radical scavenging activities for DPPH and super oxide anion (.O2-) radicals. Three new glucosyloxybenzyl 2-isobutylmalates, gymnosides VIII, IX, and X, were isolated from this natural medicine together with 58 known constituents. The stereostructures of gymnosides were elucidated on the basis of chemical and physicochemical evidence. In addition, the phenanthrene and dihydrostilbene constituents showed radical scavenging activities and suggested the following structural requirements on radical scavenging activities; a) phenanthrenes: 1) dihydrogenation at the 9,10-positions enhances the activities, 2) the 1 or 3-p-hydroxybenzyl group enhances the activities; b) dihydrostilbenes: 1) methylation of the 3'-position reduces the activities, 2) the 2- and/or 6-p-hydroxybenzyl groups enhance the activities.