Solvated electrons (e − s) which are generated at the disk of a rotating ring-disk electrode (RRDE) can be oxidized at the ring electrode; the electrons were generated at different electrode materials in a 0.3 M Li salt + hexamethylphosphortriamide (HMPA) solution. By means of this RRDE technique the current distribution during e − s generation at glassy carbon was investigated: a uniform current density distribution could not be obtained during e − s generation. Also passivation of different ring electrode materials in this medium was studied. During cathodic polarization at Pt, a film, probably from the electrocatalytically destroyed solvent, was formed. This film is impermeable for e − s. At glassy carbon, however, this type of passivation was not observed. The e − s diffusion coefficient in a 0.3 M LiBr + HMPA solution was calculated at different temperatures from − s transit time measurements. The activation energy of diffusion was found to be 5.9 kJ mol −1.