Panax ginseng C.A. Meyer (Araliaceae), mainly cultivated in Korea and Northeast China, is processed before use based on its long history of ethnopharmacological evidence. Ginsenosides have been regarded as the main active components responsible for the pharmacological activities of ginseng. Although the Maillard reaction is known as a major source of compounds related to enhanced antioxidant activity by heat treatment in various crude drugs or foods, the chemical and free radical-scavenging activity changes of ginsenosides brought about by the Maillard reaction have not yet been elucidated. This paper gives a review of our recent findings, with emphasis on the hydroxyl radical (center dot OH)-scavenging activity changes of ginsengs and ginsenosides by heat-processing using an electron spin resonance spectrometer. 20(S)-Rg(3) showed the strongest activity, and the next was in the decreasing order of Rb-1, Rg(1), Rc, Rb-2, and Rd. The center dot OH-scavenging activities of ginsenosides were related to the ferrous metal ion-chelating activities of their aglycone, 20(S)-protopanaxadiol. In addition, the ferrous metal ion-chelating activities of ginsenosides were thought to be influenced by their types of hydrophilic sugar moieties. Moreover, Rb-1 was changed into 20(S)-Rg(3), 20(R)-Rg(3), Rk(1), and Rg(5) by heat-processing, and the sugar moieties at carbon-20 were separated. The generated amount of 20(S)-Rg(3) was higher than when Rb-1 was heat-processed without amino acids, and a significant increase in Maillard reaction products was noted. Based upon chemical and center dot OH-scavenging activity tests using Maillard reaction model experiments, the scientific evidence underlying the increase in free radical-scavenging activity of ginseng induced by heat-processing was elucidated.