In this study, we investigated the reaction between electrogenerated O2 •-and RsvH3 in aprotic N,N-dimethylformamide (DMF) solution. Furthermore, the mechanism of the scavenging of O2 •- and PT-forming HO2 • by RsvH3/RsvH2 -has been inferred with the aid of density functional theory (DFT) calculations. Additionally, we focus on the mechanistic insights related to the structural characteristics of RsvH3; i.e., three OH protons, para-OH (4'OH), and the stilbene moiety. Accordingly, we present valuable information regarding the O2 •-scavenging by RsvH3, which is assumed to be important for understanding of the substantial health benefits of use, and enhancement of pharmacological use as a phytoalexin. coupled to electrochemical software (Supporting Information, Table ). The working electrode was polished with alumina paste on a polishing wheel, rinsed with deionized water and acetone, then air-dried, before the experiments. The reference electrode was calibrated using the ferrocenim ion/ferrocene couple (Fc + /Fc). In situ electrolytic ESR and UV-vis spectra were measured using a JES-X320 X-band spectrometer (JEOL Ltd., Tokyo, Japan) and an OCEAN HDX spectrometer (OptoSirius Co., Ltd., Tokyo, Japan). The controlled-potential electrolysis was performed at room temperature in two types of cells: an electrolytic ESR cell using a 0.5mm-diameter straight Pt wire sealed in a glass capillary as the working electrode, and an optically transparent thin-layer electrochemical (OTTLE) cell (path length: 1.0 mm) with a Ptmesh working electrode (Supporting Information, Figure ). Samples were prepared in a glove box filled with N2 gas to prevent contamination by moisture. The DMF solutions containing 0.1 mol dm -3 TPAP as a supporting electrolyte were saturated with O2 by air-bubbling the gas for ca.