The reaction chemistry of H-terminated (Ill)-oriented Si surfaces has been explored in the presence of one-electron oxidants in alcohol solvents. Similar chemistry was observed for Si surfaces exposed to methanolic solutions of ferrocenium tetrafluoroborate or to methanolic solutions of I-2, as well as for Si electrodes that were subjected to anodic electrochemical oxidation processes in methanol. Oxidation in alcohols activates the surficial Si-H bond toward nucleophilic attack, producing alkoxylated surfaces. This mechanism for Si-H activation is supported by infrared spectroscopy, temperature-programmed desorption spectroscopy, and by X-ray photoelectron spectroscopic studies of this system. These data explain a variety of observations regarding the surface chemistry and electrochemistry of Si electrodes and surfaces.